WO2013168616A1 - Masking material, method for manufacturing masking material, masking member, masking method, and method for manufacturing coated member - Google Patents

Masking material, method for manufacturing masking material, masking member, masking method, and method for manufacturing coated member Download PDF

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Publication number
WO2013168616A1
WO2013168616A1 PCT/JP2013/062437 JP2013062437W WO2013168616A1 WO 2013168616 A1 WO2013168616 A1 WO 2013168616A1 JP 2013062437 W JP2013062437 W JP 2013062437W WO 2013168616 A1 WO2013168616 A1 WO 2013168616A1
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Prior art keywords
masking
masking material
masked
acrylic rubber
meth
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PCT/JP2013/062437
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French (fr)
Japanese (ja)
Inventor
小野　義友
八重 石川
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リンテック株式会社
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Publication of WO2013168616A1 publication Critical patent/WO2013168616A1/en

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05B—SPRAYING APPARATUS; ATOMISING APPARATUS; NOZZLES
    • B05B12/00—Arrangements for controlling delivery; Arrangements for controlling the spray area
    • B05B12/16—Arrangements for controlling delivery; Arrangements for controlling the spray area for controlling the spray area
    • B05B12/20—Masking elements, i.e. elements defining uncoated areas on an object to be coated

Definitions

  • the present invention relates to a masking material for masking used when it is not desired to attach a paint during coating, a method for producing such a masking material, a masking member provided with such a masking material, and such a masking member.
  • the present invention relates to a masking method using a coating material and a method for producing a painted member.
  • a masking tape is generally used for masking a portion where a paint is not desired to be applied during painting.
  • the masking tape is composed of a tape base material, an adhesive layer, and a release paper.
  • the release paper is peeled off, and the masking tape is applied to the masked portion using the adhesive force of the exposed adhesive layer. Then, it is peeled off from the masked portion after painting and discarded.
  • both the release paper and the masking tape after painting are wastes to be discarded, which is a waste of resources.
  • the masking tape that has been applied once is peeled off and then reapplied, it may not be possible to reapply or the parting line may not appear clean due to a decrease in the adhesive strength of the adhesive layer.
  • a desired adhesive strength cannot be obtained unless the oil content in the masked portion is removed.
  • Patent Document 1 proposes to use a sheet containing magnetic powder as a masking sheet. According to such a masking sheet, it is possible to save the masking work by using the magnetic force.
  • the masking sheet described in Patent Document 1 is chlorinated polyethylene, nitrile rubber (NBR), ethylene-propylene-diene rubber (EPDM), chlorinated polyethylene (CPE), ethylene-vinyl acetate copolymer (EVA), chlorinated.
  • soft plastics such as sulfonated polyethylene and soft vinyl chloride are used as the main resin component, the heat resistance is low.
  • the masking sheet is deformed or melted. In particular, when the masking sheet is melted, the masking sheet is fused to the masked portion, and the masked portion is contaminated.
  • the present invention has been made in view of such a situation, and is excellent in heat resistance, that is, not easily deformed even when heated, and a masking material that can be repeatedly used. It aims at providing the manufacturing method, the masking member provided with such a masking material, the masking method using such a masking member, and the manufacturing method of a coating member.
  • the present invention completed on the basis of the above knowledge firstly includes an acrylic rubber having a crosslinked structure based on an amine-based crosslinking agent and a magnetic material, and the content of the magnetic material is based on 100 parts by mass of the acrylic rubber.
  • a masking material characterized by being 10 to 80 parts by volume (Invention 1).
  • the Shore D hardness is 10 to 40 when the integration time in a 180 ° C. environment is 13 hours (Invention 2).
  • Such a masking material further reduces the possibility that a paint or the like may enter during use between the masking material and the masked part even when the usage environment is high.
  • the acrylic rubber preferably contains a polymer having a structural unit derived from an alkoxyalkyl ester of (meth) acrylic acid (Invention 3).
  • the said acrylic rubber contains the copolymer which has a structural unit derived from the (meth) acrylic-acid alkylester and a structural unit derived from the (meth) acrylic-acid alkoxyalkylester.
  • the acrylic rubber contains the copolymer according to the inventions (Inventions 3 and 4), a masking material that is superior in heat-curing resistance can be obtained.
  • an anti-aging agent Invention 5
  • an anti-aging agent By containing an anti-aging agent, it becomes easy to obtain a masking material excellent in heat-curing resistance.
  • the bending resistance measured by the Gurley method is 6.0 N or less (Invention 6) when the sheet is molded into a sheet having a thickness of 1 mm.
  • the bending resistance is 6.0 N or less, it becomes easy to improve the followability of the masking material to the masked portion when the masking material is attached to the masked portion.
  • the breaking strength is preferably 2 MPa or more and 20 MPa or less (Invention 7).
  • the breaking strength is 2 MPa or more, even if a force that extends the masking material is applied during the masking material attachment / detachment operation, the possibility of problems such as cracking or breaking of the masking material is reduced. can do.
  • the breaking elongation when the masking material molded into a sheet having a thickness of 1 mm is stretched at 20 mm / min is 50% or more (Invention 8).
  • the elongation at break is 50% or more, even when a force for extending the masking material is applied during the attaching / detaching operation of the masking material, the possibility of causing a problem such as breaking of the masking material can be reduced. .
  • the said masking material is heat-processed in the state adhering to a to-be-masked part,
  • the said magnetic body contained in the said masking material is the heating temperature in the said heat processing. It is preferably made of a ferromagnetic material having a higher Curie temperature (Invention 9). By using such a material as the magnetic material, the masking material is unlikely to deteriorate in the masking material even when heat treatment is performed during use.
  • the member to be masked may be subjected to a coating process (Invention 10) prior to the heat treatment. Even in such a case, the masking material is unlikely to deteriorate the masking function because the magnetic material is made of a ferromagnetic material having a Curie temperature higher than the heating temperature in the heat treatment.
  • the present invention is secondly a state before the composition for forming a masking material according to any of the above inventions (Inventions 1 to 10) is molded and before the crosslinking reaction of the amine crosslinking agent proceeds.
  • the molded product having a cross-linking structure based on the amine-based crosslinking agent is obtained by heating the obtained molded product to advance the crosslinking reaction of the amine-based crosslinking agent contained in the molded product.
  • a method for producing a masking material characterized by forming a masking material containing acrylic rubber (Invention 11).
  • a masking material that is less likely to be deformed or melted even when placed in an environment at a high temperature of about 180 ° C. during use, has excellent heat-resistant curing properties, and can therefore be used repeatedly. Can be obtained.
  • a heating temperature T 1 (unit: ° C.) when heating the molded article, and a maximum heating temperature T 2 (unit: ° C.) that the masking material receives when using the masking material, Preferably satisfies the following formula (Invention 12).
  • T 1 > T 2 -30 ° C
  • the present invention is a masking member having at least one masking surface for contacting the masked portion, and the masking member is made of the masking material according to any one of the above inventions (Inventions 1 to 10).
  • a masking member is provided (Invention 13).
  • the present invention is a masking member having at least one masking surface for contacting the masked portion, wherein the masking member comprises the masking material according to any one of the inventions (Inventions 1 to 10), The masking surface is formed of the masking material, and provides a masking member (Invention 14).
  • the masking surface of the masking member according to any one of the above inventions is brought into contact with the masked portion of the masked member so that the masking member becomes the masked member.
  • a masking method characterized by being mounted is provided (Invention 15).
  • the present invention sixthly, the paint is adhered to the object to be coated comprising the masking member to which the masking material obtained by performing the masking method according to the above invention (Invention 15) is attached, A part in which a coating film is formed on the surface of the object to be coated from the paint adhered to the object to be coated, the masking material is removed from the object to be coated, and a film is not formed on the masked part of the masking member
  • a method for producing a painted member characterized in that a painted member comprising the above is obtained (Invention 16).
  • the masking material according to the present invention is excellent in heat resistance, problems such as deformation and melting hardly occur even if it is placed in an environment at a high temperature of about 180 ° C. during use.
  • the masking material according to the present invention can be applied to the masking material and the coating material even in a high temperature environment. It is difficult for paint to enter between the masking part and the unit during use. Therefore, the masking material according to the present invention can be used repeatedly.
  • the masking material manufacturing method according to the present invention can manufacture the masking material as described above. Furthermore, according to the masking method according to the present invention using the masking member provided with the masking material as described above, the masking material can be repeatedly used, and a method for producing a coated member including such a masking method as one of the steps. Can efficiently produce a painted member including a non-painted portion.
  • the masking material which concerns on one Embodiment of this invention is equipped with the masking surface which contacts a to-be-masked part, and contains the acrylic rubber and magnetic body which have a crosslinked structure based on an amine type crosslinking agent.
  • the “masked portion” means a portion to be masked, and a member including the masked portion is referred to as a “masked member”.
  • the member to be masked exhibits at least ferromagnetism as a whole.
  • Acrylic rubber means a homopolymer composed of structural units derived from (meth) acrylic acid ester or (meth) acrylic acid amide, (meth) acrylic acid ester and / or ( Copolymers composed of structural units derived from (meth) acrylic acid amides, and structural units derived from (meth) acrylic acid esters and / or (meth) acrylic acid amides and compounds other than (meth) acrylic acid esters (typical Is a compound having a polymerizable unsaturated bond, and in the present embodiment, also referred to as “other polymerizable compound”.) 1 type or 2 types selected from the group consisting of copolymers with structural units derived from It contains a polymer comprising the above and / or a crosslinking reaction product of the polymer and an amine-based crosslinking agent, and is a mechanical rubber-like elastic body. It means a material having properties.
  • (meth) acrylic acid ester means both acrylic acid ester and
  • the structure of the ester group of the (meth) acrylic acid ester used to form the acrylic rubber is not particularly limited, and may be a (meth) acrylic acid alkyl ester or has a functional group at the alkyl position (meta) ) Acrylic acid alkyl ester may be used.
  • alkyl (meth) acrylate esters include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, and 2-ethylhexyl (meth) acrylate. Etc. Among these, ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, and methyl methacrylate are preferable from the viewpoint of handling and availability.
  • Examples of the functional group possessed by the ester moiety include an alkoxy group, a hydroxyl group, an amino group, and an epoxy group.
  • Specific examples of the (meth) acrylic acid alkyl ester having such a functional group include (meth) acrylic acid alkoxyesters such as (meth) acrylic acid methoxyethyl and (meth) acrylic acid ethoxyethyl; (meth) acrylic acid 2- Hydroxyethyl, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 3-hydroxybutyl (meth) acrylate, 4-methacrylic acid 4- (Meth) acrylic acid hydroxyalkyl esters such as hydroxybutyl; (meth) acrylic acid monomethylaminoethyl, (meth) acrylic acid monoethylaminoethyl, (meth) acrylic acid monomethylaminopropyl, (meth) acrylic acid monoeth
  • examples of (meth) acrylic amide include (meth) acrylamide, N-methylacrylamide, N-methylmethacrylamide, N-methylolacrylamide, N-methylolmethacrylamide and the like.
  • the acrylic rubber preferably contains a polymer having a structural unit derived from an alkoxyalkyl ester of acrylic acid. In this case, it is easy to obtain an acrylic rubber excellent in heat-curing resistance. Moreover, it is easy to obtain acrylic rubber having high oil resistance.
  • the (meth) acrylic acid ester and (meth) acrylic acid amide used for forming the acrylic rubber may be used alone or in combination of two or more.
  • the acrylic rubber according to the present embodiment includes a component based on a copolymer having a structural unit derived from a plurality of types of (meth) acrylic acid esters
  • the (meth) acrylic acid ester is an alkyl (meth) acrylate. It is preferable to include an ester and an alkoxyalkyl ester of (meth) acrylic acid.
  • the acrylic rubber contains such a component by including a component based on a copolymer having a structural unit derived from a (meth) acrylic acid alkyl ester and a structural unit derived from a (meth) acrylic acid alkoxyalkyl ester In this case, it is easy to obtain an acrylic rubber having excellent heat resistance and excellent heat resistance.
  • the type of other polymerizable compound used for forming the acrylic rubber is not particularly limited as long as it can undergo a polymerization reaction with the (meth) acrylic acid ester. Typically, it is a compound having a polymerizable unsaturated bond as described above.
  • Such compounds include olefins such as ethylene, propylene, n-butene, norbornene, and cyclohexene; aromatic compounds having an ethylenically unsaturated bond such as styrene and derivatives thereof; (meth) acrylic acid, crotonic acid, cinnamic acid, and the like ⁇ , ⁇ -ethylenically unsaturated monocarboxylic acid having 3 to 12 carbon atoms; ⁇ , ⁇ -ethylenically unsaturated dicarboxylic acid having 4 to 12 carbon atoms such as fumaric acid, maleic acid, itaconic acid, citraconic acid; Monoesters of ⁇ , ⁇ -ethylenically unsaturated dicarboxylic acids having 3 to 11 carbon atoms and alkanols having 1 to 8 carbon atoms such as monoethyl acid, monocyclopentyl fumarate, monobutyl maleate, monobutyl itaconate
  • ⁇ , ⁇ -ethylenically unsaturated dicarboxylic acid is contained as a structural unit in the form of dicarboxylic anhydride in acrylic rubber, and is hydrolyzed during crosslinking to form a carboxyl group. May be generated.
  • compounds having a carboxyl group such as ⁇ , ⁇ -ethylenically unsaturated monocarboxylic acid and ⁇ , ⁇ -ethylenically unsaturated dicarboxylic acid can form a reaction point with the amine-based crosslinking agent described later. Therefore, it is preferable.
  • the carboxyl group in this compound may be in the form of an acid anhydride as described above.
  • the other polymerizable compounds may be used alone or in combination of two or more.
  • the proportion of the structural units derived from these compounds in the acrylic rubber is arbitrary, and the acrylic What is necessary is just to set suitably considering the use etc. of the masking material containing rubber
  • an acrylic rubber having a low embrittlement temperature tends to be obtained when the ratio of alkyl methacrylate having a bulky alkyl group such as a butyl group is high, and other polymerizable compounds having a carboxyl group tend to be obtained.
  • a hard acrylic rubber may be obtained if the degree of crosslinking reaction with the amine-based crosslinking agent is high.
  • the cross-linking agent used for forming the cross-linking structure of the acrylic rubber according to this embodiment includes an amine-based cross-linking agent.
  • the “amine-based crosslinking agent” means a bifunctional or higher amine-based compound, and is not particularly limited as long as it is a compound having two or more nitrogen atoms having at least one active hydrogen. Since the acrylic rubber according to the present embodiment has a cross-linked structure, it is prevented that the masking material according to the present embodiment is excessively softened even when exposed to a high temperature environment of 180 ° C., for example.
  • the masking material according to the present embodiment is excellent in heat-curing resistance as compared with a case where it is based on another cross-linking agent such as an isocyanate-based cross-linking agent. For this reason, even if it uses repeatedly, the masking function of a masking material does not fall easily.
  • amine-based crosslinking agents examples include 1,4-butanediamine, 1,9-nonanediamine, 2-methyl-1,8-octanediamine, 1,4-diaminocyclohexane, triethylenetetramine, tetraethylenepentamine, and ethylenediamine.
  • Aliphatic polyamines such as undecane; Aromatic polyamines such as diaminodiphenylmethane, xylylenediamine, phenylenediamine, diaminodiphenylsulfone; carbazic acid, 6-aminohexylcarbamic acid, 4,4′-methylenebis (cyclohexylamine) carbamide Amino carbamic acid and the like; further such as salts of the polyamines and amino carbamic acid.
  • the amine-based crosslinking agent may be composed of one kind of compound or may be composed of a plurality of kinds of compounds.
  • the amine-based cross-linking agent used for forming the acrylic rubber according to the present embodiment preferably contains aminocarbamic acid and / or a salt thereof from the viewpoint of improving the heat resistance.
  • the amount of the amine-based crosslinking agent used for forming the acrylic rubber is usually preferably 0.01 to 10 parts by mass with respect to 100 parts by mass of the polymer constituting the acrylic rubber. More preferably, it is 1 to 5 parts by mass.
  • the degree of the cross-linking structure based on the amine-based cross-linking agent in the acrylic rubber according to this embodiment is not particularly limited.
  • the density of cross-linking points is not particularly limited.
  • the masking material becomes too hard and difficult to deform due to the content of other components (especially magnetic substances) contained in the masking material, and masking the shape of the masked part.
  • the density of cross-linking points should be appropriately set in consideration of the composition of the material constituting the masking.
  • the content of the uncrosslinked amine-based crosslinking agent remaining in the acrylic rubber contained in the masking material according to the present embodiment is as small as possible.
  • an uncrosslinked amine-based cross-linking agent is heated during use of the masking material to cause a cross-linking reaction, the density of cross-linking points in the acrylic rubber increases during use, increasing the Shore D hardness of the masking material. Is brought about. When the degree of increase in hardness is significant, the masking function of the masking material may be lowered.
  • the acrylic rubber according to this embodiment preferably contains a crosslinking accelerator.
  • the crosslinking accelerator include amino compounds such as triethylamine and tetramethylbutanediamine, stannous chloride, dimethyltin dichloride, trimethyltin hydroxide, di-n-butyltin dilaurate, dibutyltin diacetate, dibutyltin sulfide, chloride chloride
  • Metal compounds such as ferric iron, iron acetyl acetate, cobalt naphthenate, bismuth nitrate, lead oleate, and antimony trichloride can be used.
  • Magnetic body As a material which comprises the magnetic body which the masking material which concerns on this embodiment contains, for example, metals, such as iron, nickel, cobalt, those alloys (for example, stainless steel) or oxide, or strontium ferrite Ferrites such as barium ferrite, manganese zinc ferrite, nickel zinc ferrite and copper zinc ferrite, alnicos such as aluminum-nickel-cobalt alloys, rare earth-transition metals (eg, SmCo, SmFeN, NbFeB), etc. Rare earth-based ferromagnetic materials. Among these, from the viewpoint of easy control of the magnetic force, a ferrite type is preferable, and among them, strontium ferrite and barium ferrite are more preferable.
  • metals such as iron, nickel, cobalt, those alloys (for example, stainless steel) or oxide
  • strontium ferrite Ferrites such as barium ferrite, manganese zinc ferrite, nickel zinc ferrite and copper zinc fer
  • the magnetic body is preferably made of a ferromagnetic material having a Curie temperature higher than the heating temperature in the heat treatment.
  • the shape of the magnetic material is preferably a powder shape from the viewpoint of ease of molding of the masking material.
  • the volume average particle diameter is preferably 0.1 to 100 ⁇ m, more preferably 0.3 to 50 ⁇ m, and particularly preferably 0.5 to 20 ⁇ m.
  • the volume average particle size of the powder-shaped magnetic material referred to here is a laser diffraction type particle size distribution measuring device (manufactured by Horiba, Ltd., product name: laser diffraction / scattering type particle size distribution measuring device LA-920). The volume average particle diameter measured by a measuring method based on JIS K5600-9-3.
  • the content of the magnetic substance in the masking material according to the present embodiment is 10 parts by volume or more and 80 parts by volume or less with respect to 100 parts by volume of acrylic rubber having a crosslinked structure based on an amine-based crosslinking agent. If the content is excessively large, the masking material becomes hard. Conversely, if the content is excessively low, the adhesion force based on the magnetic force of the masking material to the masked portion decreases, and in either case, the masking function decreases. However, by setting the content of the magnetic substance in the above range, it is possible to avoid a decrease in adhesion. If the content of the magnetic material is 15 parts by volume or more and 70 parts by volume or less with respect to 100 parts by volume of the acrylic rubber, the decrease in the adhesion can be avoided more stably. More preferably, it is not more than the volume part.
  • the masking material which concerns on this embodiment may contain an anti-aging agent in addition to said acrylic rubber and a magnetic body.
  • the type of anti-aging agent is not particularly limited as long as the antioxidant effect is high.
  • an amine-ketone type anti-aging agent such as a 2,2,4-trimethyl-1,2-dihydroquinoline polymer; 4 , 4-bis ( ⁇ , ⁇ -dimethylbenzyl) diphenylamine, N, N′-di-2-naphthyl-p-phenylenediamine and other aromatic secondary amine antioxidants; zinc salt of 2-mercaptobenzimidazole And benzimidazole anti-aging agents such as zinc salt of 2-mercaptomethylbenzimidazole; dithiocarbamate anti-aging agents such as nickel dibutyldithiocarbamate; and phosphite anti-aging agents such as tris (nonylphenyl) phosphate Can be mentioned.
  • the anti-aging agent may be composed of one kind or two
  • the content of the anti-aging agent is not particularly limited, and should be set as appropriate in consideration of its function and the composition of the acrylic rubber.
  • the content of the anti-aging agent is usually preferably 0.001 to 1 part by mass, more preferably 0.01 to 0.1 part by mass with respect to 100 parts by mass of the acrylic rubber.
  • the masking material which concerns on this embodiment may further contain additives, such as a dispersing agent, as other components.
  • a nonmagnetic material such as talc or kaolin may be contained for the purpose of adjusting the hardness.
  • the content of these components is not particularly limited, and may be set so as not to lower the masking function of the masking material.
  • the masking material according to the present embodiment has a Shore D hardness (also referred to as “post-heated Shore D hardness” in the present embodiment) when the accumulated time placed in an environment of 180 ° C. is 13 hours. )) Is preferably 10-40.
  • the masking material follows the shape of the masked part when the masking material is brought into contact with the masked part even when it is repeatedly used because the Shore D hardness after heating of the masking material is 40 or less. Becomes easy. From the viewpoint of stably improving the followability of the masking material to the masked portion, the Shore D hardness after heating is preferably 35 or less, and more preferably 30 or less.
  • the Shore D hardness after heating tends to be 40 or less, and if the composition is appropriately adjusted, it is sufficiently more than 30 A low value is also possible.
  • the Shore D hardness after heating of the masking material is 10 or more, it is avoided that the workability of attaching the masking material to the masked portion is significantly reduced.
  • the Shore D hardness after heating is less than 10, there is a concern that the masking material may adhere to the masked portion depending on the components of the acrylic rubber, and the masking material removal operation becomes difficult.
  • the Shore D hardness after heating of the masking material is preferably 12 or more, and more preferably 14 or more.
  • the masking material according to the present embodiment preferably has a bending softness of 6.0 N or less.
  • the “bending softness” is a bending softness measured using a Gurley type tester defined in JIS L1096 when a masking material is molded into a sheet having a thickness of 1 mm. It means the bending resistance by the Gurley method.
  • the bending resistance is 6.0 N or less, it becomes easy to improve the followability of the masking material to the masked portion when the masking material is attached to the masked portion.
  • the bending resistance of the masking material is preferably 5.5 N or less, and more preferably 5.0 N or less.
  • the bending resistance of the masking material is preferably as low as possible from the viewpoint of improving its followability, but if it is excessively low, there is a problem when the masking material is attached to or detached from the masked member as in the case of Shore D hardness described above. Therefore, the bending resistance of the masking material is usually preferably 0.5 N or more.
  • the masking material according to the present embodiment preferably has a breaking strength measured in accordance with JIS K7127 (measurement environment: 23 ° C., 50% RH) of 2 MPa or more and 20 MPa or less.
  • the breaking strength is 2 MPa or more, even if a force that extends the masking material is applied during the masking material attachment / detachment operation, the possibility of problems such as cracking or breaking of the masking material is reduced. can do.
  • the breaking strength of the masking material is more preferably 3 MPa or more, and further preferably 4 MPa or more.
  • the breaking strength of the masking material is usually preferably 20 MPa or less because the above-mentioned bending resistance may tend to increase excessively.
  • breaking elongation is preferably 50% or more.
  • breaking elongation is preferably 50% or more.
  • the breaking elongation of the masking material is preferably 60% or more, and more preferably 100% or more. From the viewpoint of avoiding the above problems, the higher the breaking elongation of the masking material, the better. However, if it is excessively high, the above-mentioned bending resistance may tend to increase excessively.
  • the elongation at break is usually preferably 2000% or less.
  • the dimensional change rate in the in-plane direction of the surface in contact with the masked portion is small.
  • the rate of dimensional change when the cumulative time under a 180 ° C. environment is 13 hours is preferably within a range of ⁇ 5.0%, particularly preferably within a range of ⁇ 3.0%.
  • the dimensional change rate of the masking material is within the above range, it can be said that the dimensional stability of the masking material is excellent. Further, in this case, since the material is not easily deformed even when heated, and particularly difficult to shrink, the masking performance after heating is excellent.
  • the manufacturing method of the masking material which concerns on this embodiment is not limited. It is appropriately set according to the composition and shape to be formed. Since the masking material has a cross-linked structure, the molded product in the state before the cross-linking reaction of the amine-based cross-linking agent obtained by molding the material for forming the masking material is heated. The method of advancing the crosslinking reaction of the amine-based crosslinking agent contained in the molded product is preferable from the viewpoint of ease of production and quality stability. An example of the method is as follows.
  • the polymer constituting the acrylic rubber, the amine-based cross-linking agent and the magnetic material, and further containing additional components such as an anti-aging agent, if necessary, are in a state before the cross-linking reaction between the polymer and the cross-linking agent proceeds.
  • a composition is prepared. Specifically, the above polymer, amine-based crosslinking agent and magnetic substance (preferably magnetic powder), and if necessary, further additives are melted using a Henschel mixer, single or twin screw extruder, Banbury mixer, roll, etc. What is necessary is just to mix. The composition is subjected to a molding process to roughly form the shape of the masking material.
  • the molding method include calendar molding, injection molding, extrusion molding, and the like, and injection molding is preferable because a molded product with high shape accuracy can be easily obtained.
  • a masking material can be obtained by heating the obtained molded article and allowing the crosslinking reaction to proceed.
  • the masking material obtained in the above manufacturing process or the obtained masking material may be magnetized by a known method.
  • the heating temperature for proceeding the crosslinking reaction should be appropriately set depending on the type of the crosslinking agent, etc. It is preferable to set the temperature equal to the maximum heating temperature (hereinafter referred to as “use temperature”) that the masking material receives when using the mask. If the crosslinking temperature is excessively lower than the use temperature, the crosslinking reaction may not be completed in the masking material manufacturing stage, and the crosslinking reaction may proceed when the masking material is heated during use of the masking material. Is done. In this case, there may be a problem that the Shore D hardness after heating is increased and the masking function is lowered. From the viewpoint of stably avoiding such a problem, it is preferable that the crosslinking temperature T 1 be higher than the use temperature T 2 -30 ° C., that is, satisfy the following formula. T 1 > T 2 -30 ° C
  • T 1 is preferably 40 ° C. or more, and more preferably 50 ° C. or more.
  • the crosslinking temperature T 1 is preferably 100 to 200 ° C., and more preferably 140 to 180 ° C.
  • the heating time for advancing the crosslinking reaction of the molded product is arbitrary, and may be appropriately set in consideration of the type of crosslinking agent and the crosslinking temperature.
  • the cross-linking reaction of the molded product is almost completed so that the cross-linking reaction proceeds in the masking material due to heating of the masking material during use and the hardness of the masking material does not increase excessively during use. In consideration of this, it is preferable to set the heating time.
  • the masking material according to the present embodiment may be a member used when performing a masking operation as it is.
  • a member having at least one masking surface for contacting the masked portion is referred to as a “masking member”.
  • the masking member according to the present embodiment includes the masking material according to the above-described embodiment, and the masking member is made of a masking material as a specific example, and the masking member is a member other than the masking material as another specific example.
  • the material constituting the masking surface is a masking material.
  • the masking member is made of a masking material
  • the masking member can be obtained by performing the above-described masking material manufacturing method, which may be advantageous from the viewpoint of productivity.
  • the portion on the masking surface side of the masking member may be composed of the aforementioned masking material, and the other portion of the masking member may be composed of other than the masking material.
  • the shape flexibility of the masking member may be increased.
  • the shape of the masking member and the shape of the masking material according to this embodiment are not particularly limited. It may be a sheet shape or a block shape. In the case of a sheet, the thickness is arbitrary, and is preferably 0.3 to 2.5 mm, more preferably 0.5 to 1.5 mm from the viewpoint of easy attachment / detachment work of the masking member. is there. Moreover, it is preferable that the surface (masking surface) which contacts a masking member and the member to be masked of a masking material is smooth. In addition, when a masking member contains components other than a masking material as mentioned above, it is preferable from a viewpoint of improving the masking function of a masking material that the components other than a masking material also contain a magnetic body.
  • the magnetic fixing force of the masking member is preferably 3 to 20 N, and particularly preferably 4 to 15 N.
  • the magnetic fixing force of the masking member is 4N or more, the possibility that the masking member attached to the member to be masked may fall off during use can be reduced. Further, since the magnetic fixing force of the masking member is 20 N or less, an operation of removing the masking member from the member to be masked for the purpose of changing the mounting position becomes easy.
  • the magnetic fixing force of the masking member is 100 mm long when a masking member (40 mm ⁇ 150 mm, thickness 1.5 mm) made of a masking material is applied to a stainless steel plate (thickness 1.5 mm, SUS430 plate) as a member to be masked.
  • a masking member 40 mm ⁇ 150 mm, thickness 1.5 mm
  • SUS430 plate stainless steel plate
  • the magnetic force of the masking member should be appropriately set according to the purpose of use, but is usually preferably 20 to 100 mT. If the magnetic force of the masking member is 20 mT or more, the possibility that the masking member attached to the member to be masked will drop off during use can be reduced. Further, when the magnetic force of the masking member is 100 mT or less, the work of removing the masking member from the member to be masked becomes easy.
  • the magnetic force here refers to a magnetic force measured by a gauss meter at a distance of 1 cm from the surface of the masking member.
  • Method for using the masking member according to the present embodiment is not limited. For example, when the masking material of the masking member is placed opposite to the masked portion of the masked member, the masking material adheres to the masked portion by the magnetic force of the masking member, and the masking member is attached to the masked member.
  • the masking member on which the masking member is mounted is subjected to heat treatment, if the Curie temperature of the magnetic material contained in the masking member is set higher than the heating temperature related to the heat treatment, The magnetic force of the masking material that causes the adhesive force to the masking portion is not significantly attenuated.
  • the masking member may be subjected to a heating process.
  • a masking member having a masking material containing a magnetic material appropriately selected as described above maintains the magnetic force even when the heat treatment is performed. Therefore, the masking member is coated by a coating process performed before the heat treatment. It is suppressed that the coating material applied other than the masking portion enters the masked portion during the heat treatment.
  • the masking member removed from the member to be masked after the heat treatment may be attached to another member to be masked and subjected to the heat treatment.
  • the masking member according to the present embodiment can maintain an excellent masking function even if such repeated use is made.
  • the masking method described above may be used in a method for manufacturing a painted member described below, or may be used in a method for manufacturing a plated member or a member subjected to blasting.
  • Manufacturing method of coating member An example of the method of manufacturing the coating member in which the coating film is not partially formed using the masking member which concerns on this embodiment comprises the following step.
  • the masking member in the masking member according to this embodiment is brought into contact with the masked portion of the masked member, and the masking member is mounted on the masked member.
  • the masked member on which the masking member is mounted is also referred to as a body to be coated.
  • the specific shape of the member to be masked is arbitrary, and housings and frames of electrical products such as portable devices, liquid crystal televisions, refrigerators, lighting fixtures; building materials such as doors and window frames; furniture such as chairs and tables;
  • the shapes of various articles such as structural members (main body, bonnet, etc.) and components (slide rails, carriers, etc.) of transportation equipment are exemplified.
  • the paint is not particularly limited. It may be a water-based paint or a solvent-based paint. Since the acrylic rubber contained in the masking material according to the present embodiment has a cross-linked structure, it is difficult for such a coating to deteriorate.
  • Adhesion step In the adhesion step, the object to be coated is brought into contact with the paint, and the paint is adhered to the object to be coated.
  • the method for contacting the paint is arbitrary. Specific examples include dip coating, spraying, roll coating, electrodeposition coating, and the like. Conditions such as the composition, temperature, and immersion time of the paint are appropriately set according to the coating method.
  • Coating film forming step a coating film is formed on the surface of the object to be coated from the paint adhering to the object to be coated through the above adhesion step.
  • This formation method is arbitrary and is usually dry. The details of this drying method should be determined by the paint, and the object to be coated may be heated or left in the atmosphere.
  • the masking member is removed from the object to be coated that has undergone the above-described coating film forming step, and the coating film is applied to the portion (corresponding to the masked portion) where the masking material of the masking member is in contact. A painted member having a portion that is not formed is obtained.
  • the masking member removed in this removal step is used in a mounting step for another object to be coated.
  • the masking member according to the present embodiment hardly maintains a masking function even after being subjected to the coating film forming step, and therefore can maintain an excellent masking function even when used repeatedly.
  • Example 1 A structural unit derived from ethyl acrylate (EA), a structural unit derived from n-butyl acrylate (BA) and a structural unit derived from methoxyethyl acrylate (MEA) in a molar ratio of 1: 7: 4. (Hereinafter, the molar ratio of these components is referred to as “acrylate molar ratio”), and further contains a copolymer containing a trace amount of a structural unit derived from a compound having a carboxy group, and 100 parts by mass of this copolymer.
  • EA ethyl acrylate
  • BA n-butyl acrylate
  • MEA methoxyethyl acrylate
  • an acrylic rubber which is composed of 1 part by mass of 6-aminohexylcarbamic acid as an amine-based cross-linking agent and is in a state before the crosslinking reaction proceeds, , 4-Bis ( ⁇ , ⁇ -dimethylbenzyl) diphenylamine, and 47 parts by volume of Stron with respect to 100 parts by volume of the above-mentioned acrylic rubber
  • a composition as a molding material by mixing magnetic material consisting um ferrite (a volume average particle diameter 16 [mu] m).
  • a molded body having a sheet shape of 1 mm thickness was obtained by magnetization and injection molding using a mold in a magnetic field.
  • the volume average particle size of the magnetic material is determined by using a laser diffraction particle size distribution measuring device (product name: Laser diffraction / scattering particle size distribution measuring device LA-920, manufactured by Horiba Seisakusho Co., Ltd.) according to JIS K5600-9. It was measured by a measurement method based on -3.
  • the obtained molded body was put into a thermostatic bath whose furnace was maintained at 170 ° C., and the molded body was heated at a crosslinking temperature of 170 ° C. for 3 hours. Thereafter, the molded body was taken out from the thermostat and allowed to cool to room temperature to obtain a test sample of the masking material.
  • Example 2 In preparing the composition in Example 1, the acrylate molar ratio was changed from 1: 7: 4 to 1: 8: 3, and the same operation as in Example 1 was performed except that no anti-aging agent was contained. A sheet-like molded product having a thickness of 1 mm was obtained from the composition.
  • a test sample of a masking material was obtained in the same manner as in Example 1 except that the obtained molded body was heated at a crosslinking temperature of 150 ° C. for 3 hours.
  • Example 2 In preparing the composition in Example 1, in place of the amine-based crosslinking agent, an operation similar to that in Example 1 except that an isocyanate-based crosslinking agent (manufactured by Nippon Polyurethane Co., Ltd., product name: Coronate L) was used as the crosslinking agent. To obtain a molded product having a thickness of 1 mm from the composition. Hereinafter, a test sample of a masking material was obtained in the same manner as in Example 1 except that the obtained molded body was heated at a crosslinking temperature of 150 ° C. for 3 hours.
  • an isocyanate-based crosslinking agent manufactured by Nippon Polyurethane Co., Ltd., product name: Coronate L
  • Example 3 In preparing the composition in Example 1, molding was carried out in the same manner as in Example 1 except that the content of the magnetic material was set to 100 parts by volume with respect to 100 parts by volume of the acrylic rubber. I got a product. Hereinafter, a test sample of a masking material was obtained in the same manner as in Example 1 except that the obtained molded body was heated at a crosslinking temperature of 150 ° C. for 3 hours.
  • Comparative Example 4 In preparing the composition in Comparative Example 1, 100 parts by volume of polyester (manufactured by Toyobo Co., Ltd., product name: perprene) without containing acrylic rubber and an amine-based crosslinking agent and 47 parts by volume of a magnetic material made of strontium ferrite were used. The composition was obtained by mixing. This composition was molded in the same manner as in Example 1 to obtain a molded product having a thickness of 1 mm, which was used as a test sample for the masking material.
  • polyester manufactured by Toyobo Co., Ltd., product name: perprene
  • Test Example 1 Immersion test A test piece in a circular sheet shape having a diameter of 30 to 50 mm was cut out from the test samples prepared in Examples and Comparative Examples, and this test piece was mounted on a steel plate (SUS430 2B). In addition, about the test piece of the comparative example 1, it affixed using a 2 kg roller. The steel plate to which the test piece is attached or stuck was immersed in a tank filled with an aqueous coating solution (liquid temperature: 23 ° C.). The steel plate was taken out 10 minutes after the start of immersion, the masking material or the masking tape was removed, and the presence or absence of the coating liquid on the masked portion of the steel plate was confirmed. The evaluation criteria are as follows. A: No adhesion F: Adhesion Evaluation results are shown in Table 1. In addition, about the test sample of the comparative example 1 evaluated as having adhesion (F) in this evaluation, evaluation after the test example 2 was not implemented.
  • Test Example 2 Measurement of Shore D Hardness after Heating
  • the test sample of the masking material prepared in Examples and Comparative Examples was subjected to a cycle in which the sample was left in an environment at 180 ° C for 40 minutes and then left in an environment at 23 ° C for 40 minutes.
  • Shore D hardness was measured before and after a heating test repeated 20 times (integrated time at 180 ° C. was 13 hours).
  • the evaluation results are shown in Table 1.
  • the test sample of Comparative Example 4 was significantly deteriorated (brittle) and could not be measured when the above heating test was performed, it was determined that it was not subject to evaluation and the hardness measurement after the heating test was not performed. It was.
  • Test Example 3 Bending softness A test piece having a length of 38 mm and a width of 25 mm was cut out from a test sample of a masking material prepared in Examples and Comparative Examples, and the bending resistance was measured using a Gurley type tester specified in JIS L1096. Was measured. The measurement results are shown in Table 1.
  • Test Example 4 Measurement of breaking strength and breaking elongation A test piece having a length of 150 mm and a width of 15 mm was cut out from a test sample of a masking material prepared in Examples and Comparative Examples, and a universal tensile testing machine (Tensilon RTA manufactured by Orientec Co., Ltd.) -T-2M) was used to measure the breaking strength and breaking elongation according to JIS K7127: 1999. The measurement conditions were as follows. Test environment: 23 ° C, 50% RH ⁇ Tensile speed: 200 mm / min Measurement method: The load and elongation when the test sample broke were measured, and the breaking strength and breaking elongation were calculated based on these results.
  • Test Example 5 Dimensional stability A test piece having a diameter of 30 mm was cut out from the test sample of the masking material prepared in the example, and the vertical and horizontal dimensions were measured and then left in an environment of 180 ° C. for 40 minutes. Thereafter, a heating test in which a cycle of leaving for 40 minutes in an environment of 23 ° C. was repeated 10 times, the dimensions of the test piece after the heating test were also measured, and the dimensional change rate before and after the heating test (reference to the heating test) was obtained. The results are shown in Table 1.
  • the masking materials obtained in Examples 1 and 2 are excellent in mechanical properties such as bending resistance, and thus hardly cause problems during the attaching / detaching operation.
  • the heat resistance was excellent because the amount of deformation was small even after the heating test.
  • there is little change in hardness before and after the heating test and since the Shore D hardness is maintained below 40 even after heating, it is excellent in heat-resistant curability and can be used repeatedly.
  • the masking material of the present invention and the masking member provided with the same are suitably used for masking in painting work or plating work.

Landscapes

  • Details Or Accessories Of Spraying Plant Or Apparatus (AREA)
  • Application Of Or Painting With Fluid Materials (AREA)
  • Processes Of Treating Macromolecular Substances (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Abstract

Provided, as a masking material that has outstanding heat resistance and can be used repeatedly, is a masking material characterized by comprising an acrylic rubber having a crosslinked structure based on the amine crosslinking agent and a magnetic body and in that the magnetic body accounts for 10-80 parts by volume inclusive relative to 100 parts by weight of the acrylic rubber. It is preferable for the Shore D hardness of the masking material to be 10-40 for a cumulative time of 13 hours in a 180°C environment. Additionally provided are a method for manufacturing the masking material, a masking member provided with the masking material, a masking method using the masking member, and a method for manufacturing a coated member.

Description

マスキング材、マスキング材の製造方法、マスキング部材、マスキング方法、および塗装部材の製造方法MASKING MATERIAL, MASKING MATERIAL MANUFACTURING METHOD, MASKING MEMBER, MASKING METHOD, AND COATING MEMBER MANUFACTURING METHOD
　本発明は、塗装時に塗料を付着させたくない場合などに使用されるマスキングするためのマスキング材、そのようなマスキング材の製造方法、そのようなマスキング材を備えるマスキング部材、ならびにそのようなマスキング部材を用いるマスキング方法および塗装部材の製造方法に関する。 The present invention relates to a masking material for masking used when it is not desired to attach a paint during coating, a method for producing such a masking material, a masking member provided with such a masking material, and such a masking member. The present invention relates to a masking method using a coating material and a method for producing a painted member.
　従来より、塗装時に塗料を付着させたくない部分をマスキングするためには、一般的にマスキングテープが使用されている。マスキングテープは、テープ基材と、粘着剤層と、剥離紙とから構成され、使用時に剥離紙を剥がし、露出した粘着剤層の粘着力を利用して被マスキング部に貼付される。そして、塗装後に被マスキング部から剥がされ、破棄される。 Conventionally, a masking tape is generally used for masking a portion where a paint is not desired to be applied during painting. The masking tape is composed of a tape base material, an adhesive layer, and a release paper. When the masking tape is used, the release paper is peeled off, and the masking tape is applied to the masked portion using the adhesive force of the exposed adhesive layer. Then, it is peeled off from the masked portion after painting and discarded.
　このようなマスキングテープでは、剥離紙も塗装後のマスキングテープも破棄対象のゴミとなるため、資源の無駄となっている。また、一度貼付したマスキングテープを剥がして、再度貼り直そうとすると、粘着剤層の粘着力の低下により、貼り直しができない場合や、見切り線がきれいに出ない場合がある。さらに、粘着剤層の粘着力によって貼付するためには、被マスキング部の油分を除去しなければ所望の粘着力が得られないため、脱脂作業を行う必要があり、煩雑である。 In such a masking tape, both the release paper and the masking tape after painting are wastes to be discarded, which is a waste of resources. Also, if the masking tape that has been applied once is peeled off and then reapplied, it may not be possible to reapply or the parting line may not appear clean due to a decrease in the adhesive strength of the adhesive layer. Furthermore, in order to stick by the adhesive strength of the pressure-sensitive adhesive layer, a desired adhesive strength cannot be obtained unless the oil content in the masked portion is removed.
　これに対し、特許文献１では、磁性粉末を含有するシートをマスキングシートとして使用することを提案している。かかるマスキングシートによれば、磁気力を利用することによって、マスキング作業の省力化を図ることができる。 On the other hand, Patent Document 1 proposes to use a sheet containing magnetic powder as a masking sheet. According to such a masking sheet, it is possible to save the masking work by using the magnetic force.
特開昭６１－２５７２５９号公報JP-A 61-257259
　しかしながら、特許文献１に記載のマスキングシートは、塩素化ポリエチレン、ニトリルゴム（ＮＢＲ）、エチレン－プロピレン－ジエンゴム（ＥＰＤＭ）、塩素化ポリエチレン（ＣＰＥ）、エチレン－酢酸ビニル共重合体（ＥＶＡ）、塩化スルホン化ポリエチレン、軟質塩化ビニル等の軟質プラスチックを主樹脂成分としているため、耐熱性が低く、例えば１６０℃の加熱工程で使用すると、マスキングシートが変形または溶融してしまうという問題がある。特にマスキングシートが溶融した場合には、当該マスキングシートが被マスキング部に融着し、被マスキング部を汚染してしまうことになる。 However, the masking sheet described in Patent Document 1 is chlorinated polyethylene, nitrile rubber (NBR), ethylene-propylene-diene rubber (EPDM), chlorinated polyethylene (CPE), ethylene-vinyl acetate copolymer (EVA), chlorinated. Since soft plastics such as sulfonated polyethylene and soft vinyl chloride are used as the main resin component, the heat resistance is low. For example, when used in a heating process at 160 ° C., there is a problem that the masking sheet is deformed or melted. In particular, when the masking sheet is melted, the masking sheet is fused to the masked portion, and the masked portion is contaminated.
　本発明は、このような実状に鑑みてなされたものであり、耐熱性、すなわち加熱されても変形しにくいこと、に優れ、かつ繰り返しの使用が可能であるマスキング材、そのようなマスキング材の製造方法、そのようなマスキング材を備えるマスキング部材、ならびにそのようなマスキング部材を用いるマスキング方法および塗装部材の製造方法を提供することを目的とする。 The present invention has been made in view of such a situation, and is excellent in heat resistance, that is, not easily deformed even when heated, and a masking material that can be repeatedly used. It aims at providing the manufacturing method, the masking member provided with such a masking material, the masking method using such a masking member, and the manufacturing method of a coating member.
　上記目的を達成するために、本発明者らが鋭意検討した結果、マスキング材を構成する材料として、アミン系架橋剤に基づく架橋構造を有するアクリルゴムを使用することにより、上記課題を解決することができることが明らかになった。 As a result of intensive studies by the present inventors in order to achieve the above object, the above problems can be solved by using acrylic rubber having a crosslinked structure based on an amine-based crosslinking agent as a material constituting the masking material. It became clear that it was possible.
　上記知見に基づき完成された本発明は、第１に、アミン系架橋剤に基づく架橋構造を有するアクリルゴムおよび磁性体を含有し、前記磁性体の含有量は前記アクリルゴム１００質量部に対して１０体積部以上８０体積部以下であることを特徴とするマスキング材を提供する(発明１)。 The present invention completed on the basis of the above knowledge firstly includes an acrylic rubber having a crosslinked structure based on an amine-based crosslinking agent and a magnetic material, and the content of the magnetic material is based on 100 parts by mass of the acrylic rubber. Provided is a masking material characterized by being 10 to 80 parts by volume (Invention 1).
　かかるマスキング材は耐熱性に優れるため、使用中に高温に環境下に置かれても変形、溶融といった問題が生じにくい。また、そのような高温に環境下に長時間置かれても硬度が上昇しにくい（本明細書において「耐熱硬化性に優れる」ともいう。）ため、使用環境が高温であっても、マスキング材と被マスキング部との間に塗料などが使用中に侵入しにくい。それゆえ、上記の発明に係るマスキング材は繰り返しの使用が可能である。 Since such a masking material is excellent in heat resistance, problems such as deformation and melting hardly occur even if it is placed in an environment at high temperature during use. In addition, since the hardness does not easily increase even when placed in such an environment at a high temperature for a long time (also referred to as “excellent in heat-resistant curability” in this specification), even if the usage environment is high, the masking material It is difficult for paint to enter between the masked part and the masked part during use. Therefore, the masking material according to the above invention can be used repeatedly.
　上記発明（発明１）において、１８０℃環境下での積算時間が１３時間であるときのショアＤ硬度が１０～４０であることが好ましい(発明２)。かかるマスキング材は、使用環境が高温であっても、マスキング材と被マスキング部との間に塗料などが使用中に侵入する可能性がさらに低減されている。 In the above invention (Invention 1), it is preferable that the Shore D hardness is 10 to 40 when the integration time in a 180 ° C. environment is 13 hours (Invention 2). Such a masking material further reduces the possibility that a paint or the like may enter during use between the masking material and the masked part even when the usage environment is high.
　上記発明（発明１，２）において、前記アクリルゴムは、（メタ）アクリル酸アルコキシアルキルエステルに由来する構成単位を有する重合体を含むことが好ましい(発明３)。 In the above inventions (Inventions 1 and 2), the acrylic rubber preferably contains a polymer having a structural unit derived from an alkoxyalkyl ester of (meth) acrylic acid (Invention 3).
　上記発明（発明１から３）において、前記アクリルゴムは、（メタ）アクリル酸アルキルエステルに由来する構成単位および（メタ）アクリル酸アルコキシアルキルエステルに由来する構成単位を有する共重合体を含むことが好ましい(発明４)。 In the said invention (invention 1 to 3), the said acrylic rubber contains the copolymer which has a structural unit derived from the (meth) acrylic-acid alkylester and a structural unit derived from the (meth) acrylic-acid alkoxyalkylester. Preferred (Invention 4).
　前記アクリルゴムが上記発明（発明３，４）に係る共重合体を含有することによって、耐熱硬化性により優れるマスキング材が得られる。 When the acrylic rubber contains the copolymer according to the inventions (Inventions 3 and 4), a masking material that is superior in heat-curing resistance can be obtained.
　上記発明（発明１から４）において、老化防止剤を含有することが好ましい(発明５)。老化防止剤を含有することにより、耐熱硬化性に優れるマスキング材が得られやすくなる。 In the above inventions (Inventions 1 to 4), it is preferable to contain an anti-aging agent (Invention 5). By containing an anti-aging agent, it becomes easy to obtain a masking material excellent in heat-curing resistance.
　上記発明（発明１から５）において、厚み１ｍｍのシート状に成型した際に、ガーレ法により測定した剛軟度が６．０Ｎ以下であることが好ましい(発明６)。剛軟度が６．０Ｎ以下であることによって、マスキング材を被マスキング部に付着させる際のマスキング材の被マスキング部への追従性を高めることが容易となる。 In the above inventions (Inventions 1 to 5), it is preferable that the bending resistance measured by the Gurley method is 6.0 N or less (Invention 6) when the sheet is molded into a sheet having a thickness of 1 mm. When the bending resistance is 6.0 N or less, it becomes easy to improve the followability of the masking material to the masked portion when the masking material is attached to the masked portion.
　上記発明（発明１から６）において、破断強度が２ＭＰａ以上２０ＭＰａ以下であることが好ましい(発明７)。破断強度が２ＭＰａ以上であることによって、マスキング材の着脱作業時にマスキング材を引き延ばすような力が付与された場合でも、マスキング材に亀裂が入ったり破断したりするなどの問題を生じる可能性を低減することができる。 In the above inventions (Inventions 1 to 6), the breaking strength is preferably 2 MPa or more and 20 MPa or less (Invention 7). When the breaking strength is 2 MPa or more, even if a force that extends the masking material is applied during the masking material attachment / detachment operation, the possibility of problems such as cracking or breaking of the masking material is reduced. can do.
　上記発明（発明１から７）において、厚み１ｍｍのシート状に成型したマスキング材を、２０ｍｍ／分で延伸したときの破断伸度が５０％以上であることが好ましい(発明８)。この破断伸度が５０％以上であることによって、マスキング材の着脱作業時にマスキング材を引き延ばすような力が付与された場合でも、マスキング材の破断などの問題を生じる可能性を低減することができる。 In the above inventions (Inventions 1 to 7), it is preferable that the breaking elongation when the masking material molded into a sheet having a thickness of 1 mm is stretched at 20 mm / min is 50% or more (Invention 8). When the elongation at break is 50% or more, even when a force for extending the masking material is applied during the attaching / detaching operation of the masking material, the possibility of causing a problem such as breaking of the masking material can be reduced. .
　上記発明（発明１から８）において、前記マスキング材は被マスキング部に付着した状態で加熱処理が施されるものであって、前記マスキング材に含有される前記磁性体は前記加熱処理における加熱温度よりも高いキュリー温度を有する強磁性体からなることが好ましい(発明９)。磁性体としてこのような材料を用いることによって、使用中に加熱処理が施される場合であってもマスキング材はマスキング機能の劣化が生じにくい。 In the said invention (invention 1-8), the said masking material is heat-processed in the state adhering to a to-be-masked part, Comprising: The said magnetic body contained in the said masking material is the heating temperature in the said heat processing. It is preferably made of a ferromagnetic material having a higher Curie temperature (Invention 9). By using such a material as the magnetic material, the masking material is unlikely to deteriorate in the masking material even when heat treatment is performed during use.
　上記発明（発明９）において、前記加熱処理に先立って、前記被マスキング部材に塗装処理が施されてもよい(発明１０)。そのような場合であっても、磁性体が加熱処理における加熱温度よりも高いキュリー温度を有する強磁性体からなることで、マスキング材はマスキング機能の劣化が生じにくい。 In the above invention (Invention 9), the member to be masked may be subjected to a coating process (Invention 10) prior to the heat treatment. Even in such a case, the masking material is unlikely to deteriorate the masking function because the magnetic material is made of a ferromagnetic material having a Curie temperature higher than the heating temperature in the heat treatment.
　本発明は、第２に、上記発明（発明１から１０）のいずれかに係るマスキング材を形成するための組成物を成形加工して、前記アミン系架橋剤の架橋反応が進行する前の状態にある成形品を得て、得られた前記成形品を加熱することにより前記成形品に含まれる前記アミン系架橋剤の架橋反応を進行させて、前記アミン系架橋剤に基づく架橋構造を有する前記アクリルゴムを含有するマスキング材を形成することを特徴とするマスキング材の製造方法を提供する（発明１１）。 The present invention is secondly a state before the composition for forming a masking material according to any of the above inventions (Inventions 1 to 10) is molded and before the crosslinking reaction of the amine crosslinking agent proceeds. The molded product having a cross-linking structure based on the amine-based crosslinking agent is obtained by heating the obtained molded product to advance the crosslinking reaction of the amine-based crosslinking agent contained in the molded product. Provided is a method for producing a masking material characterized by forming a masking material containing acrylic rubber (Invention 11).
　かかる製造方法を実施することにより、使用中に１８０℃程度の高温に環境下に置かれても変形、溶融といった問題が生じにくく、耐熱硬化性に優れ、それゆえ繰り返しの使用が可能なマスキング材を得ることができる。 By carrying out such a manufacturing method, a masking material that is less likely to be deformed or melted even when placed in an environment at a high temperature of about 180 ° C. during use, has excellent heat-resistant curing properties, and can therefore be used repeatedly. Can be obtained.
　上記発明（発明１１）において、前記成形品を加熱する際の加熱温度Ｔ１（単位：℃）と前記マスキング材を使用する際に前記マスキング材が受ける最高加熱温度Ｔ２（単位：℃）とは下記式を満たすことが好ましい（発明１２）。
　　Ｔ１＞Ｔ２－３０℃
　かかる関係を満たすことで、マスキング材が使用中に硬度が上昇してマスキング機能が低下する可能性が特に低減される。 In the above invention (Invention 11), a heating temperature T 1 (unit: ° C.) when heating the molded article, and a maximum heating temperature T 2 (unit: ° C.) that the masking material receives when using the masking material, Preferably satisfies the following formula (Invention 12).
T 1 > T 2 -30 ° C
By satisfying such a relationship, the possibility that the masking function is lowered due to an increase in hardness during use of the masking material is particularly reduced.
　本発明は、第３に、被マスキング部に接するためのマスキング面を少なくとも一つ有するマスキング部材であって、前記マスキング部材は上記発明（発明１から１０）のいずれかに係るマスキング材からなることを特徴とするマスキング部材を提供する（発明１３）。 Thirdly, the present invention is a masking member having at least one masking surface for contacting the masked portion, and the masking member is made of the masking material according to any one of the above inventions (Inventions 1 to 10). A masking member is provided (Invention 13).
　本発明は、第４に、被マスキング部に接するためのマスキング面を少なくとも一つ有するマスキング部材であって、前記マスキング部材は上記発明（発明１から１０）のいずれかに係るマスキング材を備え、前記マスキング面は前記マスキング材により構成されることを特徴とするマスキング部材を提供する（発明１４）。 Fourth, the present invention is a masking member having at least one masking surface for contacting the masked portion, wherein the masking member comprises the masking material according to any one of the inventions (Inventions 1 to 10), The masking surface is formed of the masking material, and provides a masking member (Invention 14).
　上記の発明（発明１３，１４）マスキング部材は、マスキング面を構成する材料が上記発明（発明１から１０）のマスキング材であるため、繰り返し使用されても優れたマスキング機能を維持することができる。 In the above inventions (Inventions 13 and 14), since the material constituting the masking surface is the masking material of the above inventions (Inventions 1 to 10), an excellent masking function can be maintained even when used repeatedly. .
　本発明は、第５に、上記発明（発明１３，１４）のいずれかに係るマスキング部材における前記マスキング面を、被マスキング部材の被マスキング部に接触させて、前記マスキング部材を前記被マスキング部材に装着することを特徴とするマスキング方法を提供する（発明１５）。 In the fifth aspect of the present invention, the masking surface of the masking member according to any one of the above inventions (Inventions 13 and 14) is brought into contact with the masked portion of the masked member so that the masking member becomes the masked member. A masking method characterized by being mounted is provided (Invention 15).
　かかるマスキング方法を実施することによって、被マスキング部を適切にマスキングすることが実現される。しかも、そのマスキング部材は繰り返し使用可能なものなので、マスキング方法の実施に係るコストを低減することが可能となる。 By performing such a masking method, it is possible to appropriately mask the masked portion. Moreover, since the masking member can be used repeatedly, it is possible to reduce the cost associated with the masking method.
　本発明は、第６に、上記の発明（発明１５）に係るマスキング方法を行うことにより得られた前記マスキング材が装着された前記被マスキング部材からなる被塗装体に前記塗料を付着させ、前記被塗装体に付着した前記塗料から前記被塗装体の表面に塗膜を形成し、前記被塗装体から前記マスキング材を取り外し、前記被マスキング部材の被マスキング部に塗膜が形成されていない部分を有してなる塗装部材を得ることを特徴とする塗装部材の製造方法を提供する（発明１６）。 The present invention sixthly, the paint is adhered to the object to be coated comprising the masking member to which the masking material obtained by performing the masking method according to the above invention (Invention 15) is attached, A part in which a coating film is formed on the surface of the object to be coated from the paint adhered to the object to be coated, the masking material is removed from the object to be coated, and a film is not formed on the masked part of the masking member There is provided a method for producing a painted member, characterized in that a painted member comprising the above is obtained (Invention 16).
　かかる塗装部材の製造方法を実施することによって、被マスキング部材の被マスキング部に塗膜が形成されていない部分を有してなる塗装部材を安定的にかつ経済的に得ることが実現される。 By carrying out such a method for producing a painted member, it is possible to stably and economically obtain a painted member having a portion where a coating film is not formed in the masked portion of the masked member.
　本発明に係るマスキング材は耐熱性に優れるため、使用中に１８０℃程度の高温に環境下に置かれても変形、溶融といった問題が生じにくい。また、そのような高温に環境下に長時間置かれても硬度が上昇しにくい（耐熱硬化性に優れる）ため、本発明に係るマスキング材は使用環境が高温であっても、マスキング材と被マスキング部との間に塗料などが使用中に侵入しにくい。それゆえ、本発明に係るマスキング材は繰り返しの使用が可能である。 Since the masking material according to the present invention is excellent in heat resistance, problems such as deformation and melting hardly occur even if it is placed in an environment at a high temperature of about 180 ° C. during use. In addition, since the hardness does not easily increase even when placed in such an environment at a high temperature for a long time (excellent heat-resistant curability), the masking material according to the present invention can be applied to the masking material and the coating material even in a high temperature environment. It is difficult for paint to enter between the masking part and the unit during use. Therefore, the masking material according to the present invention can be used repeatedly.
　本発明に係るマスキング材の製造方法によれば、上記のようなマスキング材を製造することができる。さらに、上記のようなマスキング材を備えるマスキング部材を用いる本発明に係るマスキング方法によればマスキング材を繰り返し使用することができ、そのようなマスキング方法を工程の一つとして含む塗装部材の製造方法は、非塗装部を含む塗装部材を効率的に製造することができる。 The masking material manufacturing method according to the present invention can manufacture the masking material as described above. Furthermore, according to the masking method according to the present invention using the masking member provided with the masking material as described above, the masking material can be repeatedly used, and a method for producing a coated member including such a masking method as one of the steps. Can efficiently produce a painted member including a non-painted portion.
　以下、本発明の実施形態について説明する。
１．マスキング材
　本発明の一実施形態に係るマスキング材は被マスキング部と接触するマスキング面を備え、アミン系架橋剤に基づく架橋構造を有するアクリルゴムおよび磁性体を含有する。
　なお、本実施形態において、「被マスキング部」とはマスキングが施される部分を意味し、被マスキング部を備える部材を「被マスキング部材」という。本実施形態では、被マスキング部材は少なくとも全体として強磁性を示すものであって、磁化された磁性体を被マスキング部に接触させると、磁気力が作用してその磁性体は被マスキング部に付着する。 Hereinafter, embodiments of the present invention will be described.
1. Masking material The masking material which concerns on one Embodiment of this invention is equipped with the masking surface which contacts a to-be-masked part, and contains the acrylic rubber and magnetic body which have a crosslinked structure based on an amine type crosslinking agent.
In the present embodiment, the “masked portion” means a portion to be masked, and a member including the masked portion is referred to as a “masked member”. In this embodiment, the member to be masked exhibits at least ferromagnetism as a whole. When a magnetized magnetic material is brought into contact with the masked portion, a magnetic force acts and the magnetic material adheres to the masked portion. To do.
（１）アクリルゴム
　本実施形態において「アクリルゴム」とは、（メタ）アクリル酸エステルまたは（メタ）アクリル酸アミドに由来する構成単位からなる単独重合体、（メタ）アクリル酸エステルおよび／または（メタ）アクリル酸アミドに由来する構成単位からなる共重合体、ならびに（メタ）アクリル酸エステルおよび／または（メタ）アクリル酸アミドに由来する構成単位と（メタ）アクリル酸エステル以外の化合物（典型的には重合性不飽和結合を有する化合物であり、本実施形態において、「その他の重合性化合物」ともいう。）に由来する構成単位との共重合体からなる群から選ばれる１種または２種以上からなる重合体および／またはその重合体とアミン系架橋剤との架橋反応生成物を含有し、ゴム状弾性体としての機械的性質を有する材料を意味する。なお、本明細書において、（メタ）アクリル酸エステルとは、アクリル酸エステルおよびメタクリル酸エステルの両方を意味する。他の類似用語も同様である。 (1) Acrylic rubber In this embodiment, “acrylic rubber” means a homopolymer composed of structural units derived from (meth) acrylic acid ester or (meth) acrylic acid amide, (meth) acrylic acid ester and / or ( Copolymers composed of structural units derived from (meth) acrylic acid amides, and structural units derived from (meth) acrylic acid esters and / or (meth) acrylic acid amides and compounds other than (meth) acrylic acid esters (typical Is a compound having a polymerizable unsaturated bond, and in the present embodiment, also referred to as “other polymerizable compound”.) 1 type or 2 types selected from the group consisting of copolymers with structural units derived from It contains a polymer comprising the above and / or a crosslinking reaction product of the polymer and an amine-based crosslinking agent, and is a mechanical rubber-like elastic body. It means a material having properties. In addition, in this specification, (meth) acrylic acid ester means both acrylic acid ester and methacrylic acid ester. The same applies to other similar terms.
　アクリルゴムを形成するために使用される（メタ）アクリル酸エステルのエステル基の構造は特に限定されず、（メタ）アクリル酸アルキルエステルであってもよいし、アルキル位に官能基を有する（メタ）アクリル酸アルキルエステルであってもよい。 The structure of the ester group of the (meth) acrylic acid ester used to form the acrylic rubber is not particularly limited, and may be a (meth) acrylic acid alkyl ester or has a functional group at the alkyl position (meta) ) Acrylic acid alkyl ester may be used.
　（メタ）アクリル酸アルキルエステルについて具体例を示せば、（メタ）アクリル酸メチル、（メタ）アクリル酸エチル、（メタ）アクリル酸プロピル、（メタ）アクリル酸ブチル、（メタ）アクリル酸２－エチルヘキシル等が挙げられる。これらの中でも、取り扱いや入手のしやすさなどの観点から、アクリル酸エチル、アクリル酸ブチル、アクリル酸２－エチルヘキシルおよびメタアクリル酸メチルが好ましい。 Specific examples of alkyl (meth) acrylate esters include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, and 2-ethylhexyl (meth) acrylate. Etc. Among these, ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, and methyl methacrylate are preferable from the viewpoint of handling and availability.
　エステル部分が有する官能基として、アルコキシ基、水酸基、アミノ基、エポキシ基などが例示される。こうした官能基を有する（メタ）アクリル酸アルキルエステルの具体例としては、（メタ）アクリル酸メトキシエチル、（メタ）アクリル酸エトキシエチル等の（メタ）アクリル酸アルコキシエステル；（メタ）アクリル酸２－ヒドロキシエチル、（メタ）アクリル酸２－ヒドロキシプロピル、（メタ）アクリル酸３－ヒドロキシプロピル、（メタ）アクリル酸２－ヒドロキシブチル、（メタ）アクリル酸３－ヒドロキシブチル、（メタ）アクリル酸４－ヒドロキシブチル等の（メタ）アクリル酸ヒドロキシアルキルエステル；（メタ）アクリル酸モノメチルアミノエチル、（メタ）アクリル酸モノエチルアミノエチル、（メタ）アクリル酸モノメチルアミノプロピル、（メタ）アクリル酸モノエチルアミノプロピル等の（メタ）アクリル酸モノアルキルアミノアルキル；（メタ）アクリル酸グリシジル、アクリル酸４－（グリシジルオキシ）ブチル等、アクリル酸(３，４－エポキシシクロヘキサン－１－イル)メチル等の（メタ）アクリル酸エポキシアルキルが例示される。 Examples of the functional group possessed by the ester moiety include an alkoxy group, a hydroxyl group, an amino group, and an epoxy group. Specific examples of the (meth) acrylic acid alkyl ester having such a functional group include (meth) acrylic acid alkoxyesters such as (meth) acrylic acid methoxyethyl and (meth) acrylic acid ethoxyethyl; (meth) acrylic acid 2- Hydroxyethyl, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 3-hydroxybutyl (meth) acrylate, 4-methacrylic acid 4- (Meth) acrylic acid hydroxyalkyl esters such as hydroxybutyl; (meth) acrylic acid monomethylaminoethyl, (meth) acrylic acid monoethylaminoethyl, (meth) acrylic acid monomethylaminopropyl, (meth) acrylic acid monoethylaminopropyl (Meth) acrylic acid such as Noalkylaminoalkyl; (meth) acrylic acid glycidyl, acrylic acid 4- (glycidyloxy) butyl, etc., and (meth) acrylic acid epoxyalkyl such as (3,4-epoxycyclohexane-1-yl) methyl acrylate are exemplified. The
　一方、（メタ）アクリル酸アミドとしては、（メタ）アクリルアミド、Ｎ－メチルアクリルアミド、Ｎ－メチルメタクリルアミド、Ｎ－メチロールアクリルアミド、Ｎ－メチロールメタクリルアミドなどが例示される。 On the other hand, examples of (meth) acrylic amide include (meth) acrylamide, N-methylacrylamide, N-methylmethacrylamide, N-methylolacrylamide, N-methylolmethacrylamide and the like.
　これらの中でも、（メタ）アクリル酸アルコキシアルキルエステルが好ましく、その中でもアクリル酸メトキシエチルが特に好ましい。すなわち、アクリルゴムは、アクリル酸アルコキシアルキルエステルに由来する構成単位を有する重合体を含むことが好ましい。この場合には、耐熱硬化性に優れるアクリルゴムが得られやすい。また、耐油性が高いアクリルゴムも得られやすい。 Among these, (meth) acrylic acid alkoxyalkyl esters are preferable, and methoxyethyl acrylate is particularly preferable. That is, the acrylic rubber preferably contains a polymer having a structural unit derived from an alkoxyalkyl ester of acrylic acid. In this case, it is easy to obtain an acrylic rubber excellent in heat-curing resistance. Moreover, it is easy to obtain acrylic rubber having high oil resistance.
　アクリルゴムを形成するために使用される（メタ）アクリル酸エステルや（メタ）アクリル酸アミドは、１種単独であってもよく、２種以上であってもよい。本実施形態に係るアクリルゴムが複数種類の（メタ）アクリル酸エステルに由来する構成単位を有する共重合体に基づく成分を含む場合には、その（メタ）アクリル酸エステルは（メタ）アクリル酸アルキルエステルおよび（メタ）アクリル酸アルコキシアルキルエステルを含むことが好ましい。アクリルゴムが（メタ）アクリル酸アルキルエステルに由来する構成単位および（メタ）アクリル酸アルコキシアルキルエステルに由来する構成単位を有する共重合体に基づく成分を含むことにより、アクリルゴムがかかる成分を含む場合には、耐熱性に優れ、かつ耐熱硬化性に優れるアクリルゴムが得られやすい。 The (meth) acrylic acid ester and (meth) acrylic acid amide used for forming the acrylic rubber may be used alone or in combination of two or more. When the acrylic rubber according to the present embodiment includes a component based on a copolymer having a structural unit derived from a plurality of types of (meth) acrylic acid esters, the (meth) acrylic acid ester is an alkyl (meth) acrylate. It is preferable to include an ester and an alkoxyalkyl ester of (meth) acrylic acid. When the acrylic rubber contains such a component by including a component based on a copolymer having a structural unit derived from a (meth) acrylic acid alkyl ester and a structural unit derived from a (meth) acrylic acid alkoxyalkyl ester In this case, it is easy to obtain an acrylic rubber having excellent heat resistance and excellent heat resistance.
　アクリルゴムを形成するために使用されるその他の重合性化合物の種類は、（メタ）アクリル酸エステルと重合反応しうる限り、特に限定されない。典型的には前述のように重合性不飽和結合を有する化合物である。そのような化合物として、エチレン、プロピレン、ｎ－ブテン、ノルボルネン、シクロヘキセンなどオレフィン類；スチレンおよびその誘導体などエチレン性不飽和結合を有する芳香族化合物；（メタ）アクリル酸、クロトン酸、ケイ皮酸などの炭素数３～１２のα，β－エチレン性不飽和モノカルボン酸；フマル酸、マレイン酸、イタコン酸、シトラコン酸などの炭素数４～１２のα，β－エチレン性不飽和ジカルボン酸；フマル酸モノエチル、フマル酸モノシクロペンチル、マレイン酸モノブチル、イタコン酸モノブチルなどの炭素数３～１１のα，β－エチレン性不飽和ジカルボン酸と炭素数１～８のアルカノールとのモノエステル；酢酸ビニル、アクリロニトリルなど化合物などが挙げられる。なお、その他の重合性化合物のうち、α，β－エチレン性不飽和ジカルボン酸は、アクリルゴム中で、ジカルボン酸無水物の形の構成単位として含有され、架橋の際に加水分解してカルボキシル基を生成してもよい。 The type of other polymerizable compound used for forming the acrylic rubber is not particularly limited as long as it can undergo a polymerization reaction with the (meth) acrylic acid ester. Typically, it is a compound having a polymerizable unsaturated bond as described above. Examples of such compounds include olefins such as ethylene, propylene, n-butene, norbornene, and cyclohexene; aromatic compounds having an ethylenically unsaturated bond such as styrene and derivatives thereof; (meth) acrylic acid, crotonic acid, cinnamic acid, and the like Α, β-ethylenically unsaturated monocarboxylic acid having 3 to 12 carbon atoms; α, β-ethylenically unsaturated dicarboxylic acid having 4 to 12 carbon atoms such as fumaric acid, maleic acid, itaconic acid, citraconic acid; Monoesters of α, β-ethylenically unsaturated dicarboxylic acids having 3 to 11 carbon atoms and alkanols having 1 to 8 carbon atoms such as monoethyl acid, monocyclopentyl fumarate, monobutyl maleate, monobutyl itaconate; vinyl acetate, acrylonitrile And the like. Of the other polymerizable compounds, α, β-ethylenically unsaturated dicarboxylic acid is contained as a structural unit in the form of dicarboxylic anhydride in acrylic rubber, and is hydrolyzed during crosslinking to form a carboxyl group. May be generated.
　これらの中でも、α，β－エチレン性不飽和モノカルボン酸、α，β－エチレン性不飽和ジカルボン酸などのカルボキシル基を有する化合物が、後述するアミン系架橋剤との反応点をなすことができるため好ましい。なお、この化合物におけるカルボキシル基は、上記のとおり酸無水物の形式であってもよい。
　アクリルゴムを形成するために他の重合性化合物が使用される場合において、その他の重合性化合物は１種単独であってもよく２種以上であってもよい。 Among these, compounds having a carboxyl group such as α, β-ethylenically unsaturated monocarboxylic acid and α, β-ethylenically unsaturated dicarboxylic acid can form a reaction point with the amine-based crosslinking agent described later. Therefore, it is preferable. The carboxyl group in this compound may be in the form of an acid anhydride as described above.
When other polymerizable compounds are used to form the acrylic rubber, the other polymerizable compounds may be used alone or in combination of two or more.
　（メタ）アクリル酸エステル、さらに必要に応じ使用されるその他の重合性化合物が複数種類の化合物からなる場合において、それらの化合物に由来する構成単位のアクリルゴム中の比率は任意であり、そのアクリルゴムを含有するマスキング材の用途などを考慮して適宜設定すればよい。例えば、ブチル基のようにアルキル基が嵩高い（メタ）アクリル酸アルキルエステルの比率が多い場合には脆化温度が低いアクリルゴムが得られる傾向があり、カルボキシル基を有するその他の重合性化合物の比率が多い場合には、アミン系架橋剤との架橋反応の程度が高いと、硬質なアクリルゴムが得られる場合がある。 In the case where the (meth) acrylic acid ester and other polymerizable compounds used as required are composed of a plurality of types of compounds, the proportion of the structural units derived from these compounds in the acrylic rubber is arbitrary, and the acrylic What is necessary is just to set suitably considering the use etc. of the masking material containing rubber | gum. For example, an acrylic rubber having a low embrittlement temperature tends to be obtained when the ratio of alkyl methacrylate having a bulky alkyl group such as a butyl group is high, and other polymerizable compounds having a carboxyl group tend to be obtained. When the ratio is large, a hard acrylic rubber may be obtained if the degree of crosslinking reaction with the amine-based crosslinking agent is high.
　本実施形態に係るアクリルゴムが有する架橋構造を形成するために使用される架橋剤は、アミン系架橋剤を含む。本実施形態において「アミン系架橋剤」とは、２官能以上のアミン系化合物を意味し、少なくとも１個以上の活性水素を有する窒素原子を２個以上有する化合物であれば特に制限はない。本実施形態に係るアクリルゴムは架橋構造を有しているため、本実施形態に係るマスキング材が例えば１８０℃の高温環境下に曝されても過度に軟化することは防止されている。また、架橋構造がアミン系架橋剤に基づくことにより、他の架橋剤、たとえばイソシアネート系の架橋剤に基づく場合に比べて、本実施形態に係るマスキング材は耐熱硬化性に優れる。このため、繰り返し使用してもマスキング材のマスキング機能が低下しにくい。 The cross-linking agent used for forming the cross-linking structure of the acrylic rubber according to this embodiment includes an amine-based cross-linking agent. In the present embodiment, the “amine-based crosslinking agent” means a bifunctional or higher amine-based compound, and is not particularly limited as long as it is a compound having two or more nitrogen atoms having at least one active hydrogen. Since the acrylic rubber according to the present embodiment has a cross-linked structure, it is prevented that the masking material according to the present embodiment is excessively softened even when exposed to a high temperature environment of 180 ° C., for example. Further, since the cross-linking structure is based on an amine-based cross-linking agent, the masking material according to the present embodiment is excellent in heat-curing resistance as compared with a case where it is based on another cross-linking agent such as an isocyanate-based cross-linking agent. For this reason, even if it uses repeatedly, the masking function of a masking material does not fall easily.
　アミン系架橋剤としては、例えば、１，４－ブタンジアミン、１，９－ノナンジアミン、２－メチル－１，８－オクタンジアミン、１，４－ジアミノシクロヘキサン、トリエチレンテトラミン、テトラエチレンペンタミン、エチレンジアミン、Ｎ，Ｎ－ジシンナミリデン－１，６－ヘキサンジアミン、トリメチレンジアミン、ヘキサメチレンジアミンカルバメート、３，９－ビス（３－アミノプロピル）－２，４，８，１０－テトラオキサ－２－スピロ［５．５］ウンデカン等の脂肪族ポリアミン；ジアミノジフェニルメタン、キシリレンジアミン、フェニレンジアミン、ジアミノジフェニルスルホン等の芳香族ポリアミン；カルバジン酸、６－アミノヘキシルカルバミド酸、４，４’－メチレンビス（シクロヘキシルアミン）カルバミド酸等のアミノカルバミド酸；さらにはこれらのポリアミンやアミノカルバミド酸の塩などが挙げられる。アミン系架橋剤は、１種類の化合物から構成されていてもよいし、複数種類の化合物から構成されていてもよい。本実施形態に係るアクリルゴムを形成するために使用されるアミン系架橋剤は、耐熱硬化性を向上させる観点からアミノカルバミド酸および／またはその塩を含むことが好ましい。 Examples of amine-based crosslinking agents include 1,4-butanediamine, 1,9-nonanediamine, 2-methyl-1,8-octanediamine, 1,4-diaminocyclohexane, triethylenetetramine, tetraethylenepentamine, and ethylenediamine. N, N-dicinnamylidene-1,6-hexanediamine, trimethylenediamine, hexamethylenediaminecarbamate, 3,9-bis (3-aminopropyl) -2,4,8,10-tetraoxa-2-spiro [5 .5] Aliphatic polyamines such as undecane; Aromatic polyamines such as diaminodiphenylmethane, xylylenediamine, phenylenediamine, diaminodiphenylsulfone; carbazic acid, 6-aminohexylcarbamic acid, 4,4′-methylenebis (cyclohexylamine) carbamide Amino carbamic acid and the like; further such as salts of the polyamines and amino carbamic acid. The amine-based crosslinking agent may be composed of one kind of compound or may be composed of a plurality of kinds of compounds. The amine-based cross-linking agent used for forming the acrylic rubber according to the present embodiment preferably contains aminocarbamic acid and / or a salt thereof from the viewpoint of improving the heat resistance.
　アクリルゴムを形成するために使用されるアミン系架橋剤の配合量は、通常、アクリルゴムを構成する重合体１００質量部に対して、０．０１～１０質量部であることが好ましく、０．１～５質量部であることがさらに好ましい。 The amount of the amine-based crosslinking agent used for forming the acrylic rubber is usually preferably 0.01 to 10 parts by mass with respect to 100 parts by mass of the polymer constituting the acrylic rubber. More preferably, it is 1 to 5 parts by mass.
　本実施形態に係るアクリルゴムにおけるアミン系架橋剤に基づく架橋構造の程度（換言すれば、架橋点の存在密度）は特に限定されない。過度に低い場合には耐熱硬化性に優れるアクリルゴムを得ることが困難となることが懸念される。一方、過度に高い場合にはマスキング材に含有される他の成分（特に磁性体）の含有量との関係で、マスキング材が過度に硬質化して変形しにくくなり、被マスキング部の形状にマスキング材が追従できなくなってマスキング機能が低下してしまうことが懸念される。したがって、架橋点の存在密度はマスキングを構成する材料の組成を考慮して、適宜設定されるべきものである。 The degree of the cross-linking structure based on the amine-based cross-linking agent in the acrylic rubber according to this embodiment (in other words, the density of cross-linking points) is not particularly limited. When it is too low, there is a concern that it will be difficult to obtain an acrylic rubber having excellent heat-resistant curability. On the other hand, if it is too high, the masking material becomes too hard and difficult to deform due to the content of other components (especially magnetic substances) contained in the masking material, and masking the shape of the masked part. There is a concern that the material cannot follow and the masking function deteriorates. Therefore, the density of cross-linking points should be appropriately set in consideration of the composition of the material constituting the masking.
　なお、本実施形態に係るマスキング材に含有されるアクリルゴム内に残留する未架橋のアミン系架橋剤の含有量は可能な限り少ないことが好ましい。かかる未架橋のアミン系架橋剤がマスキング材の使用中に加熱されて架橋反応を生じると、アクリルゴム中の架橋点の存在密度が使用中に増加することとなり、マスキング材のショアＤ硬度の上昇がもたらされる。この硬度上昇の程度が著しい場合には、マスキング材のマスキング機能の低下をもたらすおそれがある。 In addition, it is preferable that the content of the uncrosslinked amine-based crosslinking agent remaining in the acrylic rubber contained in the masking material according to the present embodiment is as small as possible. When such an uncrosslinked amine-based cross-linking agent is heated during use of the masking material to cause a cross-linking reaction, the density of cross-linking points in the acrylic rubber increases during use, increasing the Shore D hardness of the masking material. Is brought about. When the degree of increase in hardness is significant, the masking function of the masking material may be lowered.
　なお、架橋剤による架橋反応の反応を促進する観点から、本実施形態に係るアクリルゴムは架橋促進剤を含有することが好ましい。架橋促進剤としては、例えば、トリエチルアミン、テトラメチルブタンジアミンなどのアミノ化合物、塩化第一スズ、ジメチル二塩化スズ、トリメチルスズヒドロキシド、ジ－ｎ－ブチルスズジラウレート、ジブチルスズジアセテート、ジブチルスズスルフィド、塩化第二鉄、鉄アセチルアセテート、ナフテン酸コバルト、硝酸ビスマス、オレイン酸鉛、三塩化アンチモンなどの金属化合物などを用いることができる。 In addition, from the viewpoint of promoting the reaction of the crosslinking reaction by the crosslinking agent, the acrylic rubber according to this embodiment preferably contains a crosslinking accelerator. Examples of the crosslinking accelerator include amino compounds such as triethylamine and tetramethylbutanediamine, stannous chloride, dimethyltin dichloride, trimethyltin hydroxide, di-n-butyltin dilaurate, dibutyltin diacetate, dibutyltin sulfide, chloride chloride Metal compounds such as ferric iron, iron acetyl acetate, cobalt naphthenate, bismuth nitrate, lead oleate, and antimony trichloride can be used.
（２）磁性体
　本実施形態に係るマスキング材が含有する磁性体を構成する材料としては、例えば、鉄、ニッケル、コバルト等の金属やそれらの合金（例えばステンレススチール）または酸化物、あるいはストロンチウムフェライト、バリウムフェライト、マンガン亜鉛フェライト、ニッケル亜鉛フェライト、銅亜鉛フェライト等のフェライト系、アルミニウム－ニッケル－コバルト合金のようなアルニコ系、希土類－遷移金属系（例：ＳｍＣｏ系，ＳｍＦｅＮ系，ＮｂＦｅＢ系）等の希土類系などの強磁性体材料が挙げられる。これらの中でも、磁気力をコントロールすることが容易という観点から、フェライト系が好ましく、中でもストロンチウムフェライトおよびバリウムフェライトがより好ましい。 (2) Magnetic body As a material which comprises the magnetic body which the masking material which concerns on this embodiment contains, for example, metals, such as iron, nickel, cobalt, those alloys (for example, stainless steel) or oxide, or strontium ferrite Ferrites such as barium ferrite, manganese zinc ferrite, nickel zinc ferrite and copper zinc ferrite, alnicos such as aluminum-nickel-cobalt alloys, rare earth-transition metals (eg, SmCo, SmFeN, NbFeB), etc. Rare earth-based ferromagnetic materials. Among these, from the viewpoint of easy control of the magnetic force, a ferrite type is preferable, and among them, strontium ferrite and barium ferrite are more preferable.
　被マスキング部材にマスキング材を装着した状態で加熱処理が施されるものである場合には、磁性体は、この加熱処理における加熱温度よりも高いキュリー温度を有する強磁性体からなることが好ましい。このような材料を用いることによって、使用中に加熱処理が施される場合であってもマスキング材はマスキング機能の劣化が生じにくい。 When the heat treatment is performed with the masking member attached to the member to be masked, the magnetic body is preferably made of a ferromagnetic material having a Curie temperature higher than the heating temperature in the heat treatment. By using such a material, the masking material is unlikely to deteriorate in the masking function even when heat treatment is performed during use.
　磁性体の形状としては、マスキング材の成形加工のしやすさなどの観点から粉体形状が好ましい。粉体形状の場合、体積平均粒子径は、０．１～１００μｍであることが好ましく、０．３～５０μｍであることがさらに好ましく、０．５～２０μｍであることが特に好ましい。なお、ここでいう粉体形状の磁性体の体積平均粒子径とは、レーザ回折式粒度分布測定装置（堀場製作所社製、製品名：レーザ回折/散乱式粒度分布測定装置　ＬＡ－９２０）を用いて、ＪＩＳ　Ｋ５６００－９－３に準拠した測定方法により測定された体積平均粒子径をいう。 The shape of the magnetic material is preferably a powder shape from the viewpoint of ease of molding of the masking material. In the case of a powder shape, the volume average particle diameter is preferably 0.1 to 100 μm, more preferably 0.3 to 50 μm, and particularly preferably 0.5 to 20 μm. The volume average particle size of the powder-shaped magnetic material referred to here is a laser diffraction type particle size distribution measuring device (manufactured by Horiba, Ltd., product name: laser diffraction / scattering type particle size distribution measuring device LA-920). The volume average particle diameter measured by a measuring method based on JIS K5600-9-3.
　本実施形態に係るマスキング材における磁性体の含有量は、アミン系架橋剤に基づく架橋構造を有するアクリルゴム１００体積部に対して１０体積部以上８０体積部以下である。その含有量が過度に多い場合にはマスキング材が硬質化し、逆に過度に低い場合にはマスキング材の被マスキング部への磁気力に基づく付着力が低下し、いずれの場合もマスキング機能の低下をもたらすが、磁性体の含有量を上記の範囲とすることで、付着力の低下を回避することができる。磁性体の含有量をアクリルゴム１００体積部に対して１５体積部以上７０体積部以下とすれば、上記の付着力の低下をより安定的に回避することができるため好ましく、２０体積部以上６０体積部以下とすればさらに好ましい。 The content of the magnetic substance in the masking material according to the present embodiment is 10 parts by volume or more and 80 parts by volume or less with respect to 100 parts by volume of acrylic rubber having a crosslinked structure based on an amine-based crosslinking agent. If the content is excessively large, the masking material becomes hard. Conversely, if the content is excessively low, the adhesion force based on the magnetic force of the masking material to the masked portion decreases, and in either case, the masking function decreases. However, by setting the content of the magnetic substance in the above range, it is possible to avoid a decrease in adhesion. If the content of the magnetic material is 15 parts by volume or more and 70 parts by volume or less with respect to 100 parts by volume of the acrylic rubber, the decrease in the adhesion can be avoided more stably. More preferably, it is not more than the volume part.
（３）老化防止剤
　本実施形態に係るマスキング材は、上記のアクリルゴムおよび磁性体に加えて、老化防止剤を含有してもよい。老化防止剤の種類としては酸化防止効果が高ければ特に限定するものではないが、例えば、２，２，４－トリメチル－１,２－ジヒドロキノリン重合体などのアミン－ケトン系老化防止剤；４，４－ビス（α,α－ジメチルベンジル）ジフェニルアミン、Ｎ,Ｎ’－ジ－２－ナフチル－ｐ－フェニレンジアミン等の芳香族第二級アミン系老化防止剤；２－メルカプトベンツイミダゾールの亜鉛塩や２－メルカプトメチルベンツイミダゾールの亜鉛塩等のベンツイミダゾール系老化防止剤；ジブチルジチオカルバミン酸ニッケル等のジチオカルバミン酸塩系老化防止剤；トリス（ノニルフェニル）ホスフェイト等の亜リン酸系老化防止剤などが挙げられる。老化防止剤は１種から構成されていてもよいし、２種以上から構成されていてもよい。また、老化防止剤は、耐熱性などの観点から、４，４－ビス（α，α－ジメチルベンジル）ジフェニルアミンを含有することが好ましい。 (3) Anti-aging agent The masking material which concerns on this embodiment may contain an anti-aging agent in addition to said acrylic rubber and a magnetic body. The type of anti-aging agent is not particularly limited as long as the antioxidant effect is high. For example, an amine-ketone type anti-aging agent such as a 2,2,4-trimethyl-1,2-dihydroquinoline polymer; 4 , 4-bis (α, α-dimethylbenzyl) diphenylamine, N, N′-di-2-naphthyl-p-phenylenediamine and other aromatic secondary amine antioxidants; zinc salt of 2-mercaptobenzimidazole And benzimidazole anti-aging agents such as zinc salt of 2-mercaptomethylbenzimidazole; dithiocarbamate anti-aging agents such as nickel dibutyldithiocarbamate; and phosphite anti-aging agents such as tris (nonylphenyl) phosphate Can be mentioned. The anti-aging agent may be composed of one kind or two or more kinds. The anti-aging agent preferably contains 4,4-bis (α, α-dimethylbenzyl) diphenylamine from the viewpoint of heat resistance and the like.
　老化防止剤の含有量は特に限定されず、その機能やアクリルゴムの組成などを考慮して適宜設定されるべきものである。老化防止剤の含有量は、通常、アクリルゴム１００質量部に対して、０．００１～１質量部であることが好ましく、０．０１～０．１質量部であることがさらに好ましい。 The content of the anti-aging agent is not particularly limited, and should be set as appropriate in consideration of its function and the composition of the acrylic rubber. The content of the anti-aging agent is usually preferably 0.001 to 1 part by mass, more preferably 0.01 to 0.1 part by mass with respect to 100 parts by mass of the acrylic rubber.
（４）その他の成分
　本実施形態に係るマスキング材は、その他の成分として分散剤等の添加物をさらに含有していてもよい。また、その他の成分の一つとして、タルクやカオリンのような非磁性材料を硬度調整などの目的で含有してもよい。それらの成分の含有量は特に限定されず、マスキング材のマスキング機能を低下させないように設定すればよい。 (4) Other components The masking material which concerns on this embodiment may further contain additives, such as a dispersing agent, as other components. Further, as one of the other components, a nonmagnetic material such as talc or kaolin may be contained for the purpose of adjusting the hardness. The content of these components is not particularly limited, and may be set so as not to lower the masking function of the masking material.
（５）ショアＤ硬度
　本実施形態に係るマスキング材は、１８０℃の環境下に置かれた積算時間が１３時間であるときのショアＤ硬度（本実施形態において「加熱後ショアＤ硬度」ともいう。）が１０～４０であることが好ましい。マスキング材の加熱後ショアＤ硬度が４０以下であることによって、繰り返し使用した場合であっても、被マスキング部へマスキング材を接触させたときに、被マスキング部の形状にマスキング材が追従することが容易となる。この被マスキング部へのマスキング材の追従性を安定的に高める観点から、加熱後ショアＤ硬度は３５以下であることが好ましく、３０以下であればさらに好ましい。本実施形態に係るマスキング材は、マスキング材が含有するアクリルゴムがアミン系架橋剤を含有することから、加熱後ショアＤ硬度が４０以下となりやすく、組成を適切に調整すれば３０よりも十分に低い値とすることも可能である。一方、マスキング材の加熱後ショアＤ硬度が１０以上であることによって、マスキング材を被マスキング部に付着させる作業性が著しく低下することが回避される。また、加熱後ショアＤ硬度が１０未満の場合にはアクリルゴムの成分によっては被マスキング部にマスキング材が固着して、マスキング材の取り外し作業が困難となることも懸念される。被マスキング部材に対するマスキング材の着脱作業時に問題が発生することを安定的に回避する観点から、マスキング材の加熱後ショアＤ硬度は１２以上であることが好ましく、１４以上であることがさらに好ましい。 (5) Shore D hardness The masking material according to the present embodiment has a Shore D hardness (also referred to as “post-heated Shore D hardness” in the present embodiment) when the accumulated time placed in an environment of 180 ° C. is 13 hours. )) Is preferably 10-40. The masking material follows the shape of the masked part when the masking material is brought into contact with the masked part even when it is repeatedly used because the Shore D hardness after heating of the masking material is 40 or less. Becomes easy. From the viewpoint of stably improving the followability of the masking material to the masked portion, the Shore D hardness after heating is preferably 35 or less, and more preferably 30 or less. In the masking material according to this embodiment, since the acrylic rubber contained in the masking material contains an amine-based crosslinking agent, the Shore D hardness after heating tends to be 40 or less, and if the composition is appropriately adjusted, it is sufficiently more than 30 A low value is also possible. On the other hand, when the Shore D hardness after heating of the masking material is 10 or more, it is avoided that the workability of attaching the masking material to the masked portion is significantly reduced. Further, when the Shore D hardness after heating is less than 10, there is a concern that the masking material may adhere to the masked portion depending on the components of the acrylic rubber, and the masking material removal operation becomes difficult. From the viewpoint of stably avoiding the occurrence of a problem when the masking material is attached to or detached from the member to be masked, the Shore D hardness after heating of the masking material is preferably 12 or more, and more preferably 14 or more.
（６）剛軟度
　本実施形態に係るマスキング材は、剛軟度が６．０Ｎ以下であることが好ましい。なお、本実施形態において、「剛軟度」とは、マスキング材を厚み１ｍｍのシート状に成型した際に、ＪＩＳ　Ｌ１０９６に規定されるガーレ式試験機を用いて測定された剛軟度、すなわちガーレ法による剛軟度を意味する。剛軟度が６．０Ｎ以下であることによって、マスキング材を被マスキング部に付着させる際のマスキング材の被マスキング部への追従性を高めることが容易となる。この追従性をさらに安定的に高める観点から、マスキング材の剛軟度は５．５Ｎ以下であることが好ましく、５．０Ｎ以下であることがさらに好ましい。マスキング材の剛軟度はその追従性を高める観点からは低ければ低いほどよいが、過度に低い場合には、前述のショアＤ硬度の場合と同様に被マスキング部材に対するマスキング材の着脱作業時に問題が発生することが懸念されるため、マスキング材の剛軟度は通常０．５Ｎ以上とすることが好ましい。 (6) Bending softness The masking material according to the present embodiment preferably has a bending softness of 6.0 N or less. In the present embodiment, the “bending softness” is a bending softness measured using a Gurley type tester defined in JIS L1096 when a masking material is molded into a sheet having a thickness of 1 mm. It means the bending resistance by the Gurley method. When the bending resistance is 6.0 N or less, it becomes easy to improve the followability of the masking material to the masked portion when the masking material is attached to the masked portion. From the viewpoint of further stably improving the followability, the bending resistance of the masking material is preferably 5.5 N or less, and more preferably 5.0 N or less. The bending resistance of the masking material is preferably as low as possible from the viewpoint of improving its followability, but if it is excessively low, there is a problem when the masking material is attached to or detached from the masked member as in the case of Shore D hardness described above. Therefore, the bending resistance of the masking material is usually preferably 0.5 N or more.
（７）破断強度
　本実施形態に係るマスキング材は、ＪＩＳ　Ｋ７１２７に基づいて測定（測定環境：２３℃、５０％ＲＨ）した破断強度が２ＭＰａ以上２０ＭＰａ以下であることが好ましい。破断強度が２ＭＰａ以上であることによって、マスキング材の着脱作業時にマスキング材を引き延ばすような力が付与された場合でも、マスキング材に亀裂が入ったり破断したりするなどの問題を生じる可能性を低減することができる。この着脱作業時の問題発生の可能性をさらに安定的に低減する観点から、マスキング材の破断強度は３ＭＰａ以上であることがより好ましく、４ＭＰａ以上であることがさらに好ましい。一方、破断強度が過度に高い場合には、前述の剛軟度が過度に高まる傾向を示す場合があるため、マスキング材の破断強度は通常２０ＭＰａ以下とすることが好ましい。 (7) Breaking strength The masking material according to the present embodiment preferably has a breaking strength measured in accordance with JIS K7127 (measurement environment: 23 ° C., 50% RH) of 2 MPa or more and 20 MPa or less. When the breaking strength is 2 MPa or more, even if a force that extends the masking material is applied during the masking material attachment / detachment operation, the possibility of problems such as cracking or breaking of the masking material is reduced. can do. From the viewpoint of more stably reducing the possibility of problems during the attaching / detaching operation, the breaking strength of the masking material is more preferably 3 MPa or more, and further preferably 4 MPa or more. On the other hand, when the breaking strength is excessively high, the bending strength of the masking material is usually preferably 20 MPa or less because the above-mentioned bending resistance may tend to increase excessively.
（８）破断伸度
　本実施形態に係るマスキング材は、厚み１ｍｍのシート状に成型した際に、ＪＩＳ　Ｋ７１６１に基づいて測定（測定環境：２３℃、５０％ＲＨ）した、２０ｍｍ／分で延伸したときの破断伸度（以下、「破断伸度」と略記する。）が５０％以上であることが好ましい。この破断伸度が５０％以上であることによって、マスキング材の着脱作業時にマスキング材を引き延ばすような力が付与された場合でも、マスキング材の破断などの問題を生じる可能性を低減することができる。この着脱作業時の問題発生の可能性をさらに安定的に低減する観点から、マスキング材の破断伸度は６０％以上であることが好ましく、１００％以上であることが好ましい。上記の問題発生を回避する観点からはマスキング材の破断伸度は高ければ高いほどよいが、過度に高い場合には、前述の剛軟度が過度に高まる傾向を示す場合があるため、マスキング材の破断伸度は通常２０００％以下とすることが好ましい。 (8) Elongation at break The masking material according to the present embodiment was measured at 20 mm / min, measured according to JIS K7161 (measurement environment: 23 ° C., 50% RH) when molded into a 1 mm thick sheet. The breaking elongation (hereinafter abbreviated as “breaking elongation”) is preferably 50% or more. When the elongation at break is 50% or more, even when a force for extending the masking material is applied during the attaching / detaching operation of the masking material, the possibility of causing a problem such as breaking of the masking material can be reduced. . From the viewpoint of further stably reducing the possibility of problems during the attaching / detaching operation, the breaking elongation of the masking material is preferably 60% or more, and more preferably 100% or more. From the viewpoint of avoiding the above problems, the higher the breaking elongation of the masking material, the better. However, if it is excessively high, the above-mentioned bending resistance may tend to increase excessively. The elongation at break is usually preferably 2000% or less.
（９）寸法変化率
　本実施形態に係るマスキング材は使用中に加熱された場合でも、被マスキング部に接する面の面内方向の寸法変化率は小さいことが好ましい。
　ここで、上記の寸法変化率は、マスキング材の加熱前における平面方向の１辺の長さをＸ１、加熱後における平面方向の当該１辺の長さをＸ２とした時に、以下の式で表わされるものである。
　寸法変化率（％）＝｛１－（Ｘ２／Ｘ１）｝×１００
　１８０℃環境下での積算時間が１３時間であるときの上記の寸法変化率は、±５．０％の範囲内であることが好ましく、±３．０％の範囲内であることが特に好ましく、±１．５％の範囲内であることがさらに好ましい。マスキング材の寸法変化率が上記範囲内にあれば、マスキング材の寸法安定性は優れているということができる。また、この場合には、加熱されても材料が変形しにくい、特に収縮しにくいことから、加熱後におけるマスキング性能にも優れている。 (9) Dimensional Change Rate Even when the masking material according to this embodiment is heated during use, it is preferable that the dimensional change rate in the in-plane direction of the surface in contact with the masked portion is small.
Here, the dimensional change rate is expressed by the following equation when the length of one side in the plane direction before heating of the masking material is X 1 and the length of the one side in the plane direction after heating is X 2. It is represented by
Dimensional change rate (%) = {1− (X 2 / X 1 )} × 100
The rate of dimensional change when the cumulative time under a 180 ° C. environment is 13 hours is preferably within a range of ± 5.0%, particularly preferably within a range of ± 3.0%. More preferably, it is within the range of ± 1.5%. If the dimensional change rate of the masking material is within the above range, it can be said that the dimensional stability of the masking material is excellent. Further, in this case, since the material is not easily deformed even when heated, and particularly difficult to shrink, the masking performance after heating is excellent.
２．マスキング材の製造方法
　本実施形態に係るマスキング材の製造方法は限定されない。その組成や形成すべき形状に応じて適宜設定される。マスキング材が架橋構造を有していることから、マスキング材を形成するための材料を成形加工して得られた、アミン系架橋剤の架橋反応が進行する前の状態にある成形品を加熱して、その成形品に含まれるアミン系架橋剤の架橋反応を進行させる方法が、生産しやすさおよび品質の安定の観点から好ましく、その方法の一例を挙げれば次のとおりである。 2. Manufacturing method of masking material The manufacturing method of the masking material which concerns on this embodiment is not limited. It is appropriately set according to the composition and shape to be formed. Since the masking material has a cross-linked structure, the molded product in the state before the cross-linking reaction of the amine-based cross-linking agent obtained by molding the material for forming the masking material is heated. The method of advancing the crosslinking reaction of the amine-based crosslinking agent contained in the molded product is preferable from the viewpoint of ease of production and quality stability. An example of the method is as follows.
　まず、アクリルゴムを構成する重合体、アミン系架橋剤および磁性体、さらに必要に応じ老化防止剤等の添加成分を含有し、重合体と架橋剤との架橋反応が進行する前の状態にある組成物を調製する。具体的には、上記の重合体、アミン系架橋剤および磁性体（好ましくは磁性粉）、所望によりさらに添加物をヘンシェルミキサー、単軸または二軸押出機、バンバリーミキサー、ロール等を用いて溶融混合すればよい。この組成物に対して成形加工を施してマスキング材の形状を概略形成する。成形方法として具体的には、カレンダー成形、射出成形、押出成形などが例示され、高い形状精度の成形品を容易に得ることができることから射出成形が好ましい。得られた成形品を加熱して架橋反応を進行させることにより、マスキング材を得ることができる。なお、磁性体が磁化していない場合には、上記の製造過程において、または得られたマスキング材を公知の方法で磁化すればよい。 First, the polymer constituting the acrylic rubber, the amine-based cross-linking agent and the magnetic material, and further containing additional components such as an anti-aging agent, if necessary, are in a state before the cross-linking reaction between the polymer and the cross-linking agent proceeds. A composition is prepared. Specifically, the above polymer, amine-based crosslinking agent and magnetic substance (preferably magnetic powder), and if necessary, further additives are melted using a Henschel mixer, single or twin screw extruder, Banbury mixer, roll, etc. What is necessary is just to mix. The composition is subjected to a molding process to roughly form the shape of the masking material. Specific examples of the molding method include calendar molding, injection molding, extrusion molding, and the like, and injection molding is preferable because a molded product with high shape accuracy can be easily obtained. A masking material can be obtained by heating the obtained molded article and allowing the crosslinking reaction to proceed. When the magnetic material is not magnetized, the masking material obtained in the above manufacturing process or the obtained masking material may be magnetized by a known method.
　上記の一例に係る方法において、架橋反応を進行させるための加熱温度（以下、「架橋温度」という。）は架橋剤の種類などにより適宜設定されるべきものであるが、架橋温度は、マスキング材を使用する際にマスキング材が受ける最高加熱温度（以下、「使用温度」という。）と同等の温度とすることが好ましい。架橋温度が使用温度よりも過度に低い場合には、マスキング材の製造段階で架橋反応が完了せずに、マスキング材の使用中にマスキング材が加熱されたときに架橋反応が進行することが懸念される。この場合には、前述の加熱後ショアＤ硬度が高くなってマスキング機能が低下してしまうなどの不具合が生じることがある。かかる問題を安定的に回避する観点から、架橋温度Ｔ１は、使用温度Ｔ２－３０℃超であること、すなわち下記式を満たすことが好ましい。
　　Ｔ１＞Ｔ２－３０℃ In the method according to the above example, the heating temperature for proceeding the crosslinking reaction (hereinafter referred to as “crosslinking temperature”) should be appropriately set depending on the type of the crosslinking agent, etc. It is preferable to set the temperature equal to the maximum heating temperature (hereinafter referred to as “use temperature”) that the masking material receives when using the mask. If the crosslinking temperature is excessively lower than the use temperature, the crosslinking reaction may not be completed in the masking material manufacturing stage, and the crosslinking reaction may proceed when the masking material is heated during use of the masking material. Is done. In this case, there may be a problem that the Shore D hardness after heating is increased and the masking function is lowered. From the viewpoint of stably avoiding such a problem, it is preferable that the crosslinking temperature T 1 be higher than the use temperature T 2 -30 ° C., that is, satisfy the following formula.
T 1 > T 2 -30 ° C
　上記の問題をさらに安定的に回避する観点からは、温度差ΔＴ（＝Ｔ１－Ｔ２）は４０℃以上であることが好ましく、５０℃以上であることがさらに好ましい。ただし、架橋温度Ｔ１が過度に高い場合には、成形品が加熱中に基台に固着するなどの問題が生じる可能性があるため、この点を考慮して架橋温度Ｔ１を設定することが好ましい。架橋温度Ｔ１としては、１００～２００℃であることが好ましく、１４０～１８０℃であることがさらに好ましい。成形品の架橋反応を進行させるための加熱時間は任意であり、架橋剤の種類や架橋温度を考慮して適宜設定すればよい。この場合においても、マスキング材が使用中に加熱されたことによってマスキング材内で架橋反応が進行してマスキング材の硬度が使用中に過度に高まらないように、成形品の架橋反応をほぼ完了させることを考慮してこの加熱時間を設定することが好ましい。 From the viewpoint of avoiding the above problem more stably, the temperature difference ΔT (= T 1 −T 2 ) is preferably 40 ° C. or more, and more preferably 50 ° C. or more. However, when the crosslinking temperature T 1 is excessively high, there is a possibility that problems such as the molded product to stick to the base during the heating occurs, setting the crosslinking temperature T 1 of in consideration of this point Is preferred. The crosslinking temperature T 1 is preferably 100 to 200 ° C., and more preferably 140 to 180 ° C. The heating time for advancing the crosslinking reaction of the molded product is arbitrary, and may be appropriately set in consideration of the type of crosslinking agent and the crosslinking temperature. Even in this case, the cross-linking reaction of the molded product is almost completed so that the cross-linking reaction proceeds in the masking material due to heating of the masking material during use and the hardness of the masking material does not increase excessively during use. In consideration of this, it is preferable to set the heating time.
３．マスキング部材
　本実施形態に係るマスキング材は、そのままの形態でマスキング作業を行う際に使用する部材としてもよい。本実施形態において、そのような、被マスキング部に接するためのマスキング面を少なくとも一つ有する部材を「マスキング部材」という。本実施形態に係るマスキング部材は、前述の本実施形態に係るマスキング材を備え、具体的な一例としてマスキング部材はマスキング材からなり、他の具体的な一例として、マスキング部材はマスキング材以外の部材も備えるが、マスキング面を構成する材料はマスキング材である。 3. Masking Member The masking material according to the present embodiment may be a member used when performing a masking operation as it is. In this embodiment, such a member having at least one masking surface for contacting the masked portion is referred to as a “masking member”. The masking member according to the present embodiment includes the masking material according to the above-described embodiment, and the masking member is made of a masking material as a specific example, and the masking member is a member other than the masking material as another specific example. The material constituting the masking surface is a masking material.
　マスキング部材がマスキング材からなる場合には、前述のマスキング材の製造方法を行うことによってマスキング部材が得られるため、生産性の観点から有利な場合がある。 When the masking member is made of a masking material, the masking member can be obtained by performing the above-described masking material manufacturing method, which may be advantageous from the viewpoint of productivity.
　一方、マスキング部材の前記マスキング面側の部分が前述のマスキング材から構成され、マスキング部材におけるその他の部分はマスキング材以外から構成されていてもよい。マスキング部材がこのような構成を有する場合には、マスキング部材の形状自由度が高まる場合がある。 On the other hand, the portion on the masking surface side of the masking member may be composed of the aforementioned masking material, and the other portion of the masking member may be composed of other than the masking material. When the masking member has such a configuration, the shape flexibility of the masking member may be increased.
　本実施形態に係るマスキング部材の形状およびマスキング材の形状は、いずれも特に限定されない。シート状であってもよいし、ブロック状であってもよい。シート状である場合におけるその厚さは任意であり、マスキング部材の着脱作業のしやすさの観点から０．３～２．５ｍｍであることが好ましく、さらに好ましくは０．５～１．５ｍｍである。また、マスキング部材およびマスキング材の被マスキング部材と接する面（マスキング面）は平滑であることが好ましい。なお、上記のようにマスキング部材がマスキング材以外の構成要素を含む場合には、マスキング材以外の構成要素も磁性体を含有していることが、マスキング材のマスキング機能を高める観点から好ましい。 The shape of the masking member and the shape of the masking material according to this embodiment are not particularly limited. It may be a sheet shape or a block shape. In the case of a sheet, the thickness is arbitrary, and is preferably 0.3 to 2.5 mm, more preferably 0.5 to 1.5 mm from the viewpoint of easy attachment / detachment work of the masking member. is there. Moreover, it is preferable that the surface (masking surface) which contacts a masking member and the member to be masked of a masking material is smooth. In addition, when a masking member contains components other than a masking material as mentioned above, it is preferable from a viewpoint of improving the masking function of a masking material that the components other than a masking material also contain a magnetic body.
　被マスキング部材がステンレス板からなる場合を一例とすると、マスキング部材の磁気的固定力は、３～２０Ｎであることが好ましく、特に４～１５Ｎであることが好ましい。マスキング部材の磁気的固定力が４Ｎ以上であることにより、被マスキング部材に装着されたマスキング部材が使用中に脱落する可能性を低減することができる。また、マスキング部材の磁気的固定力が２０Ｎ以下であることにより、装着位置を変更する目的でマスキング部材を被マスキング部材から取り外す作業等が容易となる。 Taking as an example the case where the member to be masked is made of a stainless steel plate, the magnetic fixing force of the masking member is preferably 3 to 20 N, and particularly preferably 4 to 15 N. When the magnetic fixing force of the masking member is 4N or more, the possibility that the masking member attached to the member to be masked may fall off during use can be reduced. Further, since the magnetic fixing force of the masking member is 20 N or less, an operation of removing the masking member from the member to be masked for the purpose of changing the mounting position becomes easy.
　ここで、マスキング部材の磁気的固定力は、被マスキング部材としてのステンレス板（厚み１．５ｍｍ，ＳＵＳ４３０板）に、マスキング材からなるマスキング部材（４０ｍｍ×１５０ｍｍ，厚み１．５ｍｍ）を１００ｍｍ長で貼り付け（残りの５０ｍｍは把持部分）、マスキング部材をステンレス板に貼り付けた状態で、引張試験機によりステンレス板の主面内方向と平行な方向に速度３００ｍｍ／ｍｉｎで引張り、測定した値である。 Here, the magnetic fixing force of the masking member is 100 mm long when a masking member (40 mm × 150 mm, thickness 1.5 mm) made of a masking material is applied to a stainless steel plate (thickness 1.5 mm, SUS430 plate) as a member to be masked. In a state where the pasting (the remaining 50 mm is the gripping part) and the masking member is pasted on the stainless steel plate, the tensile tester was pulled in a direction parallel to the main surface direction of the stainless steel plate at a speed of 300 mm / min. is there.
　マスキング部材の磁気力はその使用目的に応じて適宜設定されるべきものであるが、通常、２０～１００ｍＴであることが好ましい。マスキング部材の磁気力が２０ｍＴ以上であれば、被マスキング部材に装着されたマスキング部材が使用中に脱落する可能性を低減することができる。また、マスキング部材の磁気力が１００ｍＴ以下であることにより、マスキング部材を被マスキング部材から取り外す作業が容易となる。ここでいう磁気力とは、マスキング部材の表面から１ｃｍ離れた距離でガウスメーターにより測定した磁気力をいう。 The magnetic force of the masking member should be appropriately set according to the purpose of use, but is usually preferably 20 to 100 mT. If the magnetic force of the masking member is 20 mT or more, the possibility that the masking member attached to the member to be masked will drop off during use can be reduced. Further, when the magnetic force of the masking member is 100 mT or less, the work of removing the masking member from the member to be masked becomes easy. The magnetic force here refers to a magnetic force measured by a gauss meter at a distance of 1 cm from the surface of the masking member.
４．マスキング部材の使用方法
　本実施形態に係るマスキング部材の使用方法は限定されない。一例を挙げれば、被マスキング部材の被マスキング部に対してマスキング部材のマスキング材を対向配置すると、マスキング部材の磁気力によってマスキング材は被マスキング部に付着し、マスキング部材は被マスキング部材に装着される。 4). Method for Using Masking Member The method for using the masking member according to the present embodiment is not limited. For example, when the masking material of the masking member is placed opposite to the masked portion of the masked member, the masking material adheres to the masked portion by the magnetic force of the masking member, and the masking member is attached to the masked member. The
　このマスキング部材が装着された被マスキング部材に対して加熱処理が施されても、マスキング部材に含有される磁性体のキュリー温度をこの加熱処理に係る加熱温度よりも高く設定しておけば、被マスキング部への付着力をもたらすマスキング材の磁気力が著しく減衰することはない。ここで、マスキング部材が装着された被マスキング部材に対して塗装処理が施されたのち、被マスキング部材に対して加熱処理を施されてもよい。上記のとおり適切に選択された磁性体を含有するマスキング材を備えるマスキング部材は加熱処理が施されても磁気力を維持するため、加熱処理の前に行われた塗装処理により被マスキング部材の被マスキング部以外に塗布された塗料が加熱処理中に被マスキング部に侵入することは抑制されている。 Even if the masking member on which the masking member is mounted is subjected to heat treatment, if the Curie temperature of the magnetic material contained in the masking member is set higher than the heating temperature related to the heat treatment, The magnetic force of the masking material that causes the adhesive force to the masking portion is not significantly attenuated. Here, after the masking member on which the masking member is mounted is subjected to a coating process, the masking member may be subjected to a heating process. A masking member having a masking material containing a magnetic material appropriately selected as described above maintains the magnetic force even when the heat treatment is performed. Therefore, the masking member is coated by a coating process performed before the heat treatment. It is suppressed that the coating material applied other than the masking portion enters the masked portion during the heat treatment.
　加熱処理が終了して被マスキング部材から取り外されたマスキング部材を、別の被マスキング部材に装着して、加熱処理を施してもよい。本実施形態に係るマスキング部材はこのような繰り返しの使用がなされても優れたマスキング機能を維持することができる。以上説明したマスキング方法は、次に説明する塗装部材の製造方法に用いてもよいし、めっき部材やブラスト処理が施された部材の製造方法などに用いてもよい。 The masking member removed from the member to be masked after the heat treatment may be attached to another member to be masked and subjected to the heat treatment. The masking member according to the present embodiment can maintain an excellent masking function even if such repeated use is made. The masking method described above may be used in a method for manufacturing a painted member described below, or may be used in a method for manufacturing a plated member or a member subjected to blasting.
５．塗装部材の製造方法
　本実施形態に係るマスキング部材を用いて部分的に塗膜が形成されていない塗装部材を製造する方法の一例は次のステップを備える。 5. Manufacturing method of coating member An example of the method of manufacturing the coating member in which the coating film is not partially formed using the masking member which concerns on this embodiment comprises the following step.
（１）装着ステップ（マスキング方法）
　装着ステップでは、本実施形態に係るマスキング部材におけるマスキング材を、被マスキング部材の被マスキング部に接触させて、マスキング部材を被マスキング部材に装着する。本実施形態に係る塗装部材の製造方法において、マスキング部材が装着された被マスキング部材を被塗装体ともいう。ここで、被マスキング部材の具体的な形状は任意であり、携帯機器、液晶テレビ、冷蔵庫、照明器具等の電気製品の筺体やフレーム；ドア、窓枠等の建材；いす、テーブル等の家具；輸送機器の構造部材（メインボディ、ボンネット等）や構成部品（スライドレール、キャリア等）など様々な物品の形状が例示される。また、塗料についても特に限定されない。水性塗料であってもよいし溶剤系の塗料であってもよい。本実施形態に係るマスキング材に含有されるアクリルゴムは架橋構造を備えるため、こうした塗料による劣化が生じにくい。 (1) Wearing step (masking method)
In the mounting step, the masking member in the masking member according to this embodiment is brought into contact with the masked portion of the masked member, and the masking member is mounted on the masked member. In the method for manufacturing a painted member according to the present embodiment, the masked member on which the masking member is mounted is also referred to as a body to be coated. Here, the specific shape of the member to be masked is arbitrary, and housings and frames of electrical products such as portable devices, liquid crystal televisions, refrigerators, lighting fixtures; building materials such as doors and window frames; furniture such as chairs and tables; The shapes of various articles such as structural members (main body, bonnet, etc.) and components (slide rails, carriers, etc.) of transportation equipment are exemplified. Also, the paint is not particularly limited. It may be a water-based paint or a solvent-based paint. Since the acrylic rubber contained in the masking material according to the present embodiment has a cross-linked structure, it is difficult for such a coating to deteriorate.
（２）付着ステップ
　付着ステップでは、上記の被塗装体を塗料に接触させて、被塗装体に塗料を付着させる。塗料の接触方法は任意である。具体例として、浸漬塗布、スプレー、ロールコート、電着塗装などが例示される。塗料の組成、温度、浸漬時間などの条件は、塗装方法に応じて適宜設定される。 (2) Adhesion step In the adhesion step, the object to be coated is brought into contact with the paint, and the paint is adhered to the object to be coated. The method for contacting the paint is arbitrary. Specific examples include dip coating, spraying, roll coating, electrodeposition coating, and the like. Conditions such as the composition, temperature, and immersion time of the paint are appropriately set according to the coating method.
（３）塗膜形成ステップ
　塗膜形成ステップでは、上記の付着ステップを経て被塗装体に付着した塗料から被塗装体の表面に塗膜を形成する。この形成方法は任意であり、通常は乾燥である。この乾燥方法の詳細は塗料により決定されるべきものであって、塗料が付着している被塗装体を加熱してもよいし、大気中に放置してもよい。 (3) Coating film forming step In the coating film forming step, a coating film is formed on the surface of the object to be coated from the paint adhering to the object to be coated through the above adhesion step. This formation method is arbitrary and is usually dry. The details of this drying method should be determined by the paint, and the object to be coated may be heated or left in the atmosphere.
（４）取り外しステップ
　取り外しステップでは、上記の塗膜形成ステップを経た被塗装体からマスキング部材を取り外し、マスキング部材のマスキング材が接触していた部分（被マスキング部に相当する。）に塗膜が形成されていない部分を有してなる塗装部材を得る。 (4) Removal step In the removal step, the masking member is removed from the object to be coated that has undergone the above-described coating film forming step, and the coating film is applied to the portion (corresponding to the masked portion) where the masking material of the masking member is in contact. A painted member having a portion that is not formed is obtained.
　本実施形態に係る製造方法の好ましい一態様では、この取り外しステップで取り外されたマスキング部材を、別の被塗装体を対象とする装着ステップにおいて使用する。上記のとおり、本実施形態に係るマスキング部材は塗膜形成ステップを経てもマスキング機能の低下が起こりにくいため、繰り返し使用されても優れたマスキング機能を維持することができる。 In a preferred aspect of the manufacturing method according to the present embodiment, the masking member removed in this removal step is used in a mounting step for another object to be coated. As described above, the masking member according to the present embodiment hardly maintains a masking function even after being subjected to the coating film forming step, and therefore can maintain an excellent masking function even when used repeatedly.
　以上説明した実施形態は、本発明の理解を容易にするために記載されたものであって、本発明を限定するために記載されたものではない。したがって、上記実施形態に開示された各要素は、本発明の技術的範囲に属する全ての設計変更や均等物をも含む趣旨である。 The embodiment described above is described for facilitating understanding of the present invention, and is not described for limiting the present invention. Therefore, each element disclosed in the above embodiment is intended to include all design changes and equivalents belonging to the technical scope of the present invention.
　以下、実施例等により本発明をさらに具体的に説明するが、本発明の範囲はこれらの実施例等に限定されるものではない。 Hereinafter, the present invention will be described more specifically with reference to examples and the like, but the scope of the present invention is not limited to these examples and the like.
〔実施例１〕
　アクリル酸エチル（ＥＡ）に由来する構成単位、アクリル酸ｎ－ブチル（ＢＡ）に由来する構成単位およびアクリル酸メトキシエチル（ＭＥＡ）に由来する構成単位をモル比として１：７：４の割合で含有し（以下、これらの成分のモル比を「アクリレートモル比」という。）、さらにカルボキシ基を有する化合物に由来する構成単位を微量含んでなる共重合体と、この共重合体１００質量部に対して１質量部のアミン系架橋剤としての６－アミノヘキシルカルバミド酸とからなり架橋反応が進行する前の状態にあるアクリルゴム、このアクリルゴム１００質量部に対して０．５質量部の４，４－ビス（α,α－ジメチルベンジル）ジフェニルアミンからなる老化防止剤、および上記のアクリルゴム１００体積部に対して４７体積部のストロンチウムフェライトからなる磁性体（体積平均粒子径１６μｍ）を混合して成形原料としての組成物を得た。この組成物を用いて、磁場中にある金型を用いた着磁ならびに射出成形により、厚さ１ｍｍのシート形状を有する成形体を得た。なお、上記の磁性体の体積平均粒子径は、レーザ回折式粒度分布測定装置（堀場製作所社製、製品名：レーザ回折/散乱式粒度分布測定装置　ＬＡ－９２０）を用いて、ＪＩＳ　Ｋ５６００－９－３に準拠した測定方法により測定した。
　得られた成形体を炉内が１７０℃に保持された恒温槽内に入れ、架橋温度を１７０℃として成形体を３時間加熱した。その後、恒温槽から成形体を取り出し、室温になるまで放冷して、マスキング材のテストサンプルを得た。 [Example 1]
A structural unit derived from ethyl acrylate (EA), a structural unit derived from n-butyl acrylate (BA) and a structural unit derived from methoxyethyl acrylate (MEA) in a molar ratio of 1: 7: 4. (Hereinafter, the molar ratio of these components is referred to as “acrylate molar ratio”), and further contains a copolymer containing a trace amount of a structural unit derived from a compound having a carboxy group, and 100 parts by mass of this copolymer. On the other hand, an acrylic rubber which is composed of 1 part by mass of 6-aminohexylcarbamic acid as an amine-based cross-linking agent and is in a state before the crosslinking reaction proceeds, , 4-Bis (α, α-dimethylbenzyl) diphenylamine, and 47 parts by volume of Stron with respect to 100 parts by volume of the above-mentioned acrylic rubber To obtain a composition as a molding material by mixing magnetic material consisting um ferrite (a volume average particle diameter 16 [mu] m). Using this composition, a molded body having a sheet shape of 1 mm thickness was obtained by magnetization and injection molding using a mold in a magnetic field. The volume average particle size of the magnetic material is determined by using a laser diffraction particle size distribution measuring device (product name: Laser diffraction / scattering particle size distribution measuring device LA-920, manufactured by Horiba Seisakusho Co., Ltd.) according to JIS K5600-9. It was measured by a measurement method based on -3.
The obtained molded body was put into a thermostatic bath whose furnace was maintained at 170 ° C., and the molded body was heated at a crosslinking temperature of 170 ° C. for 3 hours. Thereafter, the molded body was taken out from the thermostat and allowed to cool to room temperature to obtain a test sample of the masking material.
〔実施例２〕
　実施例１における組成物を調製するにあたり、アクリレートモル比を１：７：４から１：８：３に変更し、老化防止剤を含有させなかった以外は実施例１と同様の操作を行って組成物から厚さ１ｍｍのシート状の成形品を得た。以下、得られた成形体を、架橋温度を１５０℃として３時間加熱した以外は、実施例１と同様にしてマスキング材のテストサンプルを得た。 [Example 2]
In preparing the composition in Example 1, the acrylate molar ratio was changed from 1: 7: 4 to 1: 8: 3, and the same operation as in Example 1 was performed except that no anti-aging agent was contained. A sheet-like molded product having a thickness of 1 mm was obtained from the composition. Hereinafter, a test sample of a masking material was obtained in the same manner as in Example 1 except that the obtained molded body was heated at a crosslinking temperature of 150 ° C. for 3 hours.
〔比較例１〕
　従来のマスキングテープ（スリーエム社製、製品名：ファインラインマスキングテープ２８００）を用意し、これをテストサンプルとした。 [Comparative Example 1]
A conventional masking tape (manufactured by 3M, product name: Fineline Masking Tape 2800) was prepared and used as a test sample.
〔比較例２〕
　実施例１における組成物を調製するにあたり、アミン系架橋剤に代えて、イソシアネート系架橋剤（日本ポリウレタン社製、製品名：コロネートＬ）を架橋剤として用いた以外は実施例１と同様の操作を行って組成物から厚さ１ｍｍの成形品を得た。以下、得られた成形体を、架橋温度を１５０℃として３時間加熱した以外は、実施例１と同様にしてマスキング材のテストサンプルを得た。 [Comparative Example 2]
In preparing the composition in Example 1, in place of the amine-based crosslinking agent, an operation similar to that in Example 1 except that an isocyanate-based crosslinking agent (manufactured by Nippon Polyurethane Co., Ltd., product name: Coronate L) was used as the crosslinking agent. To obtain a molded product having a thickness of 1 mm from the composition. Hereinafter, a test sample of a masking material was obtained in the same manner as in Example 1 except that the obtained molded body was heated at a crosslinking temperature of 150 ° C. for 3 hours.
〔比較例３〕
　実施例１における組成物を調製するにあたり、磁性体の含有量をアクリルゴム１００体積部に対して１００体積部とした以外は実施例１と同様の操作を行って組成物から厚さ１ｍｍの成形品を得た。以下、得られた成形体を、架橋温度を１５０℃として３時間加熱した以外は、実施例１と同様にしてマスキング材のテストサンプルを得た。 [Comparative Example 3]
In preparing the composition in Example 1, molding was carried out in the same manner as in Example 1 except that the content of the magnetic material was set to 100 parts by volume with respect to 100 parts by volume of the acrylic rubber. I got a product. Hereinafter, a test sample of a masking material was obtained in the same manner as in Example 1 except that the obtained molded body was heated at a crosslinking temperature of 150 ° C. for 3 hours.
〔比較例４〕
　比較例１における組成物を調製するにあたり、アクリルゴムおよびアミン系架橋剤を含有させずにポリエステル（東洋紡績社製、製品名：ペルプレン）１００体積部とストロンチウムフェライトからなる磁性体４７体積部とを混合して組成物を得た。この組成物について実施例１と同様の成形を行って厚さ１ｍｍの成形品を得て、これをマスキング材のテストサンプルとした。 [Comparative Example 4]
In preparing the composition in Comparative Example 1, 100 parts by volume of polyester (manufactured by Toyobo Co., Ltd., product name: perprene) without containing acrylic rubber and an amine-based crosslinking agent and 47 parts by volume of a magnetic material made of strontium ferrite were used. The composition was obtained by mixing. This composition was molded in the same manner as in Example 1 to obtain a molded product having a thickness of 1 mm, which was used as a test sample for the masking material.
〔試験例１〕浸漬試験
　実施例および比較例で作成したテストサンプルから直径３０～５０ｍｍの円形シート状の試験片を切り出し、この試験片を鋼板（ＳＵＳ４３０　２Ｂ）に装着した。なお、比較例１の試験片については２ｋｇのローラーを用いて貼り付けた。試験片が装着または貼付する鋼板を、水系塗装液（液温：２３℃）を満たした槽に浸漬させた。浸漬開始から１０分後に鋼板を取り出し、マスキング材またはマスキングテープを取り外し、鋼板におけるマスキングした部分における塗装液の付着の有無を確認した。評価基準は次のとおりである。
　　Ａ：付着無し
　　Ｆ：付着あり
　評価結果を表１に示す。なお、この評価において付着あり（Ｆ）と評価された比較例１のテストサンプルについては、試験例２以降の評価を実施しなかった。 [Test Example 1] Immersion test A test piece in a circular sheet shape having a diameter of 30 to 50 mm was cut out from the test samples prepared in Examples and Comparative Examples, and this test piece was mounted on a steel plate (SUS430 2B). In addition, about the test piece of the comparative example 1, it affixed using a 2 kg roller. The steel plate to which the test piece is attached or stuck was immersed in a tank filled with an aqueous coating solution (liquid temperature: 23 ° C.). The steel plate was taken out 10 minutes after the start of immersion, the masking material or the masking tape was removed, and the presence or absence of the coating liquid on the masked portion of the steel plate was confirmed. The evaluation criteria are as follows.
A: No adhesion F: Adhesion Evaluation results are shown in Table 1. In addition, about the test sample of the comparative example 1 evaluated as having adhesion (F) in this evaluation, evaluation after the test example 2 was not implemented.
〔試験例２〕加熱後ショアＤ硬度の測定
　実施例および比較例で作成したマスキング材のテストサンプルについて、１８０℃の環境下に４０分間放置した後２３℃の環境下に４０分間放置するサイクルを２０回繰り返す加熱試験（１８０℃環境下での積算時間は１３時間）の前後でショアＤ硬度を測定した。評価結果を表１に示す。なお、比較例４のテストサンプルは、上記の加熱試験を行ったところ著しく劣化（脆化）して測定が不可能であったため、評価対象外と判定して加熱試験後の硬度測定を行わなかった。 [Test Example 2] Measurement of Shore D Hardness after Heating The test sample of the masking material prepared in Examples and Comparative Examples was subjected to a cycle in which the sample was left in an environment at 180 ° C for 40 minutes and then left in an environment at 23 ° C for 40 minutes. Shore D hardness was measured before and after a heating test repeated 20 times (integrated time at 180 ° C. was 13 hours). The evaluation results are shown in Table 1. In addition, since the test sample of Comparative Example 4 was significantly deteriorated (brittle) and could not be measured when the above heating test was performed, it was determined that it was not subject to evaluation and the hardness measurement after the heating test was not performed. It was.
〔試験例３〕剛軟度
　実施例および比較例で作成したマスキング材のテストサンプルから長さ３８ｍｍ、幅２５ｍｍの試験片を切り出し、ＪＩＳ　Ｌ１０９６に規定されるガーレ式試験機を用いて剛軟度の測定を行った。測定結果を表１に示す。 [Test Example 3] Bending softness A test piece having a length of 38 mm and a width of 25 mm was cut out from a test sample of a masking material prepared in Examples and Comparative Examples, and the bending resistance was measured using a Gurley type tester specified in JIS L1096. Was measured. The measurement results are shown in Table 1.
〔試験例４〕破断強度および破断伸度の測定
　実施例および比較例で作成したマスキング材のテストサンプルから長さ１５０ｍｍ、幅１５ｍｍの試験片を切り出し、万能引張試験機（オリエンテック社製テンシロンＲＴＡ－Ｔ－２Ｍ）を用いて、ＪＩＳ　Ｋ７１２７：１９９９に準拠して、破断強度および破断伸度の測定を行った。
　測定条件は次の通りとした。
　・試験環境：２３℃、５０％ＲＨ
　・引張速度：２００ｍｍ／ｍｉｎ
　・測定方法：テストサンプルが破断した際の荷重および伸び量を測定し、これらの結果に基づき破断強度および破断伸度を算出した。 [Test Example 4] Measurement of breaking strength and breaking elongation A test piece having a length of 150 mm and a width of 15 mm was cut out from a test sample of a masking material prepared in Examples and Comparative Examples, and a universal tensile testing machine (Tensilon RTA manufactured by Orientec Co., Ltd.) -T-2M) was used to measure the breaking strength and breaking elongation according to JIS K7127: 1999.
The measurement conditions were as follows.
Test environment: 23 ° C, 50% RH
・ Tensile speed: 200 mm / min
Measurement method: The load and elongation when the test sample broke were measured, and the breaking strength and breaking elongation were calculated based on these results.
〔試験例５〕寸法安定性
　実施例で作成したマスキング材のテストサンプルから直径３０ｍｍの試験片を切り出し、その縦方向および横方向の寸法を測定した後、１８０℃の環境下に４０分間放置した後２３℃の環境下に４０分間放置するサイクルを１０回繰り返す加熱試験を行い、加熱試験後の試験片の寸法も測定し、加熱試験前後の寸法変化率（加熱試験前基準）を求めた。その結果を表１に示す。 [Test Example 5] Dimensional stability A test piece having a diameter of 30 mm was cut out from the test sample of the masking material prepared in the example, and the vertical and horizontal dimensions were measured and then left in an environment of 180 ° C. for 40 minutes. Thereafter, a heating test in which a cycle of leaving for 40 minutes in an environment of 23 ° C. was repeated 10 times, the dimensions of the test piece after the heating test were also measured, and the dimensional change rate before and after the heating test (reference to the heating test) was obtained. The results are shown in Table 1.
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
　表１から分かるように、実施例１および２で得られたマスキング材は、剛軟度などの機械的特性に優れるため、着脱作業時に問題を生じにくいものであった。また、加熱試験を経ても変形量が少なかったことから耐熱性に優れるものであった。しかも、加熱試験前後での硬度変化が少なく、加熱後であってもショアＤ硬度が４０未満を維持していることから耐熱硬化性に優れ繰り返しの使用が可能なものであった。 As can be seen from Table 1, the masking materials obtained in Examples 1 and 2 are excellent in mechanical properties such as bending resistance, and thus hardly cause problems during the attaching / detaching operation. In addition, the heat resistance was excellent because the amount of deformation was small even after the heating test. In addition, there is little change in hardness before and after the heating test, and since the Shore D hardness is maintained below 40 even after heating, it is excellent in heat-resistant curability and can be used repeatedly.
　本発明のマスキング材およびこれを備えるマスキング部材は、塗装作業やめっき作業などにおけるマスキングに好適に用いられる。 The masking material of the present invention and the masking member provided with the same are suitably used for masking in painting work or plating work.

Claims (16)

  1. 　アミン系架橋剤に基づく架橋構造を有するアクリルゴムおよび磁性体を含有し、前記磁性体の含有量は前記アクリルゴム１００質量部に対して１０体積部以上８０体積部以下であることを特徴とするマスキング材。 An acrylic rubber having a crosslinked structure based on an amine-based crosslinking agent and a magnetic material are contained, and the content of the magnetic material is 10 to 80 parts by volume with respect to 100 parts by mass of the acrylic rubber. Masking material.
  2. 　１８０℃環境下での積算時間が１３時間であるときのショアＤ硬度が１０～４０である、請求項１に記載のマスキング材。 The masking material according to claim 1, wherein the Shore D hardness is 10 to 40 when the accumulated time in a 180 ° C environment is 13 hours.
  3. 　前記アクリルゴムは、（メタ）アクリル酸アルコキシアルキルエステルに由来する構成単位を有する重合体を含む、請求項１または２に記載のマスキング材。 The masking material according to claim 1 or 2, wherein the acrylic rubber contains a polymer having a structural unit derived from an alkoxyalkyl ester of (meth) acrylic acid.
  4. 　前記アクリルゴムは、（メタ）アクリル酸アルキルエステルに由来する構成単位および（メタ）アクリル酸アルコキシアルキルエステルに由来する構成単位を有する共重合体を含む、請求項１から３のいずれか一項に記載のマスキング材。 The acrylic rubber includes a copolymer having a structural unit derived from a (meth) acrylic acid alkyl ester and a structural unit derived from a (meth) acrylic acid alkoxyalkyl ester, according to any one of claims 1 to 3. The masking material described.
  5. 　老化防止剤を含有する、請求項１から４のいずれか一項に記載のマスキング材。 The masking material according to any one of claims 1 to 4, comprising an anti-aging agent.
  6. 　厚み１ｍｍのシート状に成型した際に、ガーレ法により測定した剛軟度が６．０Ｎ以下である、請求項１から５のいずれか一項に記載のマスキング材。 The masking material according to any one of claims 1 to 5, wherein the bending resistance measured by the Gurley method is 6.0 N or less when molded into a sheet having a thickness of 1 mm.
  7. 　破断強度が２ＭＰａ以上２０ＭＰａ以下である、請求項１から６のいずれか一項に記載のマスキング材。 The masking material according to any one of claims 1 to 6, wherein the breaking strength is 2 MPa or more and 20 MPa or less.
  8. 　厚み１ｍｍのシート状に成型したマスキング材を、２０ｍｍ／分で延伸したときの破断伸度が５０％以上である、請求項１から７のいずれか一項に記載のマスキング材。 The masking material according to any one of claims 1 to 7, wherein a breaking elongation when the masking material molded into a sheet having a thickness of 1 mm is stretched at 20 mm / min is 50% or more.
  9. 　前記マスキング材は被マスキング部に付着した状態で加熱処理が施されるものであって、前記マスキング材に含有される前記磁性体は前記加熱処理における加熱温度よりも高いキュリー温度を有する強磁性体からなる、請求項１から８のいずれか一項に記載のマスキング材。 The masking material is heat-treated while adhering to the masked portion, and the magnetic substance contained in the masking material has a Curie temperature higher than the heating temperature in the heat treatment. The masking material according to claim 1, comprising:
  10. 　前記加熱処理に先立って、前記被マスキング部材に塗装処理が施される、請求項９に記載のマスキング材。 The masking material according to claim 9, wherein the masking member is subjected to a coating process prior to the heat treatment.
  11. 　請求項１から１０のいずれか一項に記載されるマスキング材を形成するための組成物を成形加工して、前記アミン系架橋剤の架橋反応が進行する前の状態にある成形品を得て、得られた前記成形品を加熱することにより前記成形品に含まれる前記アミン系架橋剤の架橋反応を進行させて、前記アミン系架橋剤に基づく架橋構造を有する前記アクリルゴムを含有するマスキング材を形成することを特徴とするマスキング材の製造方法。 A molding for forming the masking material according to any one of claims 1 to 10 is molded to obtain a molded product in a state before the crosslinking reaction of the amine-based crosslinking agent proceeds. A masking material containing the acrylic rubber having a cross-linking structure based on the amine-based cross-linking agent by causing the cross-linking reaction of the amine-based cross-linking agent contained in the molded product to proceed by heating the obtained molded product A process for producing a masking material, characterized in that
  12. 　前記成形品を加熱する際の加熱温度Ｔ１（単位：℃）と前記マスキング材を使用する際に前記マスキング材が受ける最高加熱温度Ｔ２（単位：℃）とは下記式を満たす、請求項１１に記載の製造方法。
    　　Ｔ１＞Ｔ２－３０℃     The heating temperature T 1 (unit: ° C) when heating the molded article and the maximum heating temperature T 2 (unit: ° C) received by the masking material when using the masking material satisfy the following formula: 11. The production method according to 11.
    T 1 > T 2 -30 ° C
  13. 　被マスキング部に接するためのマスキング面を少なくとも一つ有するマスキング部材であって、前記マスキング部材は請求項１から１０のいずれか一項に記載されるマスキング材からなることを特徴とするマスキング部材。 A masking member having at least one masking surface for contacting a portion to be masked, wherein the masking member is made of the masking material according to any one of claims 1 to 10.
  14. 　被マスキング部に接するためのマスキング面を少なくとも一つ有するマスキング部材であって、前記マスキング部材は請求項１から１０のいずれか一項に記載されるマスキング材を備え、前記マスキング面は前記マスキング材により構成されることを特徴とするマスキング部材。 A masking member having at least one masking surface for contacting a masked portion, wherein the masking member includes the masking material according to any one of claims 1 to 10, wherein the masking surface is the masking material. A masking member comprising:
  15. 　請求項１３または１４に記載されるマスキング部材における前記マスキング面を、被マスキング部材の被マスキング部に接触させて、前記マスキング部材を前記被マスキング部材に装着することを特徴とするマスキング方法。 A masking method comprising mounting the masking member on the masked member by bringing the masking surface of the masking member according to claim 13 or 14 into contact with a masked portion of the masked member.
  16. 　請求項１５に記載されるマスキング方法を行うことにより得られた前記マスキング材が装着された前記被マスキング部材からなる被塗装体に前記塗料を付着させ、前記被塗装体に付着した前記塗料から前記被塗装体の表面に塗膜を形成し、前記被塗装体から前記マスキング材を取り外し、前記被マスキング部材の被マスキング部に塗膜が形成されていない部分を有してなる塗装部材を得ることを特徴とする塗装部材の製造方法。 The said coating material is made to adhere to the to-be-coated body which consists of the said to-be-masked member with which the said masking material obtained by performing the masking method described in Claim 15, and the said coating material adhere | attached on the said to-be-coated body Forming a coating film on the surface of the object to be coated, removing the masking material from the object to be coated, and obtaining a coating member having a portion where the coating film is not formed on the masked portion of the member to be masked The manufacturing method of the coating member characterized by this.
PCT/JP2013/062437 2012-05-07 2013-04-26 Masking material, method for manufacturing masking material, masking member, masking method, and method for manufacturing coated member WO2013168616A1 (en)

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CN106068316A (en) * 2014-03-07 2016-11-02 琳得科株式会社 Heat-curing type adhesive composite and heat-curing type adhesive sheet
WO2023166271A1 (en) * 2022-03-04 2023-09-07 Jet Metal Technologies Method for producing selectively metallised three-dimensional items with a masking coating composition
FR3133193A1 (en) * 2022-03-04 2023-09-08 Jet Metal Technologies COMPOSITION FOR PRODUCING MASK COATING FOR THE MANUFACTURE OF THREE-DIMENSIONAL ARTICLES WITH METAL PATTERN(S)

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JP2009209268A (en) * 2008-03-04 2009-09-17 Nippon Zeon Co Ltd Acrylic rubber, crosslinkable acrylic rubber composition, and crosslinked product thereof
JP2012076007A (en) * 2010-09-30 2012-04-19 Lintec Corp Masking material, method for producing masking material, and masking method

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JPS6362575A (en) * 1986-09-01 1988-03-18 C I Kasei Co Ltd Magnet sheet for masking
JP2001232252A (en) * 2000-02-25 2001-08-28 Asahi Rubber Kk Masking material for steel pipe coating
JP2004143573A (en) * 2002-10-25 2004-05-20 Masakatsu Yanagida Method for treating thermally sprayed metallic film on surface of non-metal formed body
JP2006156423A (en) * 2003-07-09 2006-06-15 Bridgestone Corp Rubber magnet sheet and its production method
JP2009209268A (en) * 2008-03-04 2009-09-17 Nippon Zeon Co Ltd Acrylic rubber, crosslinkable acrylic rubber composition, and crosslinked product thereof
JP2012076007A (en) * 2010-09-30 2012-04-19 Lintec Corp Masking material, method for producing masking material, and masking method

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Publication number Priority date Publication date Assignee Title
CN106068316A (en) * 2014-03-07 2016-11-02 琳得科株式会社 Heat-curing type adhesive composite and heat-curing type adhesive sheet
WO2023166271A1 (en) * 2022-03-04 2023-09-07 Jet Metal Technologies Method for producing selectively metallised three-dimensional items with a masking coating composition
FR3133193A1 (en) * 2022-03-04 2023-09-08 Jet Metal Technologies COMPOSITION FOR PRODUCING MASK COATING FOR THE MANUFACTURE OF THREE-DIMENSIONAL ARTICLES WITH METAL PATTERN(S)

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