WO2012099125A1 - ハードコート被膜付き樹脂基板およびその製造方法 - Google Patents
ハードコート被膜付き樹脂基板およびその製造方法 Download PDFInfo
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- WO2012099125A1 WO2012099125A1 PCT/JP2012/050865 JP2012050865W WO2012099125A1 WO 2012099125 A1 WO2012099125 A1 WO 2012099125A1 JP 2012050865 W JP2012050865 W JP 2012050865W WO 2012099125 A1 WO2012099125 A1 WO 2012099125A1
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- silyl group
- organopolysiloxane
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- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/04—Coating
- C08J7/043—Improving the adhesiveness of the coatings per se, e.g. forming primers
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- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
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- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D1/00—Processes for applying liquids or other fluent materials
- B05D1/36—Successively applying liquids or other fluent materials, e.g. without intermediate treatment
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- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
- B05D7/02—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials to macromolecular substances, e.g. rubber
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- B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
- B32B27/302—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising aromatic vinyl (co)polymers, e.g. styrenic (co)polymers
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- B32B27/308—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising acrylic (co)polymers
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
- C09D183/04—Polysiloxanes
- C09D183/06—Polysiloxanes containing silicon bound to oxygen-containing groups
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- B32B2255/10—Coating on the layer surface on synthetic resin layer or on natural or synthetic rubber layer
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- B60—VEHICLES IN GENERAL
- B60J—WINDOWS, WINDSCREENS, NON-FIXED ROOFS, DOORS, OR SIMILAR DEVICES FOR VEHICLES; REMOVABLE EXTERNAL PROTECTIVE COVERINGS SPECIALLY ADAPTED FOR VEHICLES
- B60J1/00—Windows; Windscreens; Accessories therefor
- B60J1/20—Accessories, e.g. wind deflectors, blinds
- B60J1/2094—Protective means for window, e.g. additional panel or foil, against vandalism, dirt, wear, shattered glass, etc.
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- C08J2433/04—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters
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- C08J2433/04—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters
- C08J2433/06—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters of esters containing only carbon, hydrogen, and oxygen, the oxygen atom being present only as part of the carboxyl radical
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Definitions
- the present invention relates to a resin substrate with a hard coat film and a method for producing the same.
- the problem of impact resistance of the primer layer itself and the adhesion between the primer layer and the hard coat layer are insufficient.
- problems in weather resistance such as the occurrence of cracks after long-term use and a decrease in adhesion as a whole.
- adhesion between the primer layer and the silicone-based hard coat layer is lowered and peeling is likely to occur.
- Patent Document 1 discloses a primer using a copolymer type polymer of ⁇ -methacryloxypropyltrimethoxysilane and a reactive ultraviolet absorber.
- a resin substrate with a hard coat layer in which a layer is formed has been proposed.
- Patent Document 2 proposes a resin substrate with a hard coat layer in which a primer layer is formed from a copolymerized polymer of methyl methacrylate, ⁇ -acryloxypropyltrimethoxysilane, and a reactive ultraviolet absorber.
- Patent Document 3 discloses a hard coat for a coating member formed by laminating a primer layer and a hard coat layer on a resin base material for the purpose of improving the adhesion and crack resistance of the film.
- the primer layer contains a thermosetting acrylic resin and a thermoplastic acrylic resin in a weight ratio of 95: 5 to 30:70.
- the adhesion between the primer layer and the silicone hard coat layer in a high humidity environment is not sufficient, and particularly accelerated weathering tests with severe humidity conditions In some cases, peeling may occur between the primer layer and the hard coat layer.
- Japanese Unexamined Patent Publication No. 2001-47574 Japanese Unexamined Patent Publication No. 4-120181 Japanese Unexamined Patent Publication No. 2006-240294
- the present invention has been made to solve the above-mentioned problems of the prior art, and in a resin substrate with a hard coat film in which a silicone-based hard coat layer is provided on a resin substrate via a primer layer, the scratch resistance is improved.
- Hard coat that is excellent in weather resistance such as adhesion after accelerated weathering test (hereinafter also referred to as “weather resistance”) and crack resistance after weathering test (hereinafter also referred to as “weather cracking resistance”). It aims at providing the resin substrate with a film.
- the resin substrate with a hard coat film according to the present invention includes a primer layer containing, as main components, an acrylic polymer (P) and a silyl group-containing acrylic polymer ( ⁇ ) on at least one surface of the resin substrate, and organopolysiloxane A hard coat layer having a hard coat layer containing as a main component a hard coat layer in order from the resin substrate side, wherein the acrylic polymer (P) has an alkyl group having 1 to 6 carbon atoms.
- the acrylic polymer (P) 90 to 100 mol% of the entire polymerized units constituting the acrylic polymer (P) are polymerized units based on methyl methacrylate, and the silyl group-containing acrylic polymer ( ⁇ ) Are polymerized units based on methyl methacrylate (MMA) and hydrolyzable silyl groups.
- MMA methyl methacrylate
- the acrylic polymer ( ⁇ ) does not contain a polymer unit having an aromatic hydrocarbon group in the side chain, and the mass ratio of the acrylic polymer (P) and the silyl group-containing acrylic polymer ( ⁇ ), that is, ( Value of acrylic polymer (P)) / (total content of acrylic polymer (P) content and silyl group-containing acrylic polymer ( ⁇ )) ⁇ 100 value is 50 to 98% by mass It is characterized by being.
- the silyl group-containing acrylic polymer ( ⁇ ) is a polymer unit having the hydrolyzable silyl group and / or SiOH group in an amount of 5 to 50 mol of the entire polymer units constituting the silyl group-containing acrylic polymer ( ⁇ ). It is preferable to contain it in the ratio of%.
- the silyl group-containing acrylic polymer ( ⁇ ) comprises a polymerized unit based on the methyl methacrylate (MMA) and a polymerized unit having the hydrolyzable silyl group and / or SiOH group, and the methyl methacrylate (
- the molar ratio of the polymerized units based on MMA) and the polymerized units having hydrolyzable silyl groups and / or SiOH groups is preferably 50:50 to 95: 5.
- the polymerized unit having a hydrolyzable silyl group and / or SiOH group includes 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyldimethylmethoxysilane, 3-methacryloxy. Composed of propyltriethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-acryloxypropyltrimethoxysilane and 3-acryloxypropylmethyldimethoxysilane, and polymerized units based on these hydrolysates or partial hydrolysates It is preferably at least one selected from the group. Moreover, it is preferable that the said silyl group containing acrylic polymer ((alpha)) does not contain the polymerization unit which has a hydroxyalkyl group.
- the acrylic polymer (P) is preferably composed of polymerized units based on methyl methacrylate.
- the silyl group-containing acrylic polymer ( ⁇ ) preferably has a mass average molecular weight of 5,000 to 300,000.
- the mass average molecular weight of the acrylic polymer (P) as the main component of the primer layer is preferably 20,000 to 1,500,000.
- the method for producing a resin substrate with a hard coat film comprises a primer layer containing, as main components, an acrylic polymer (P) and a silyl group-containing acrylic polymer ( ⁇ ) on at least one surface of the resin substrate.
- a step of applying a forming composition and drying to form a primer layer; and a hard coat layer forming composition containing organopolysiloxane as a main component is applied on the primer layer and cured to harden the hard coat layer
- the acrylic polymer (P) comprises polymerized units based on a methacrylic acid alkyl ester having an alkyl group having 1 to 6 carbon atoms.
- the silyl group-containing acrylic polymer ( ⁇ ) is a polymer unit based on methyl methacrylate (MMA), and a polymer unit having a hydrolyzable silyl group and / or SiOH group in the side chain, 50 to 95 mol% of the entire polymerized units constituting the silyl group-containing acrylic polymer ( ⁇ ) are polymerized units based on methyl methacrylate (MMA), and the silyl group-containing acrylic polymer ( ⁇ ) is aromatic.
- the term “to” indicating the above numerical range is used in the sense that the numerical values described before and after it are used as the lower limit value and the upper limit value, and unless otherwise specified, “to” is the same in the following specification. Used with meaning.
- the “hard coat film” refers to a multi-layer film including a hard coat layer formed on a resin substrate. That is, in the present invention, the entire film having the primer layer and the hard coat layer is referred to as “hard coat film”.
- the “hydrolyzable silyl group” refers to a silyl group having a hydrolyzable group directly bonded to a silicon atom.
- the “hydrolyzable group” refers to a group that becomes a hydroxyl group (—OH group) by hydrolysis. Therefore, the “hydrolyzable silyl group and / or SiOH group” means a silyl group in which a hydrolyzable group is bonded to a silicon atom, including those partially hydrolyzed to a hydroxyl group (—OH group). means.
- the “hydrolyzable silyl group and / or SiOH group” can also be described as “having at least one group selected from the group of hydrolyzable silyl groups and SiOH groups”. Specific examples of the hydrolyzable group will be described in detail later.
- the resin substrate with a hard coat film of the present invention is excellent in scratch resistance and weather resistance such as weather adhesion and weather cracking. Further, according to the method for producing a resin substrate with a hard coat film of the present invention, a resin substrate with a hard coat film having excellent scratch resistance and weather resistance such as weather adhesion and weather cracking can be obtained. .
- FIG. 1 shows an embodiment of a resin substrate with a hard coat film of the present invention.
- This resin substrate 1 with a hard coat film comprises a primer layer 3 containing an acrylic polymer (P) and a silyl group-containing acrylic polymer ( ⁇ ) as main components on at least one surface of a resin substrate 2, organopolysiloxane
- the hard coat layer 4 containing the cured product as a main component is laminated in this order.
- the acrylic polymer (P) is contained in the primer layer, the adhesion between the resin substrate 2 and the hard coat layer 4 can be improved. Furthermore, the acrylic polymer is a thermoplastic resin, is supple compared with the cross-linked polymer, and has excellent followability to the deformation of the resin substrate 2, so that it is considered that defects are hardly generated in the durability test.
- the hydrolyzable silyl group of the silyl group-containing acrylic polymer ( ⁇ ) contained in the primer layer 3 is a reactive end group (for example, the T group) that constitutes the hard coat layer 4 (for example, , Si—OX group (wherein —OX represents a hydroxyl group or an alkoxy group) to form a siloxane bond (—O—Si—O—), and therefore, between the primer layer 3 and the hard coat layer 4.
- Adhesion, particularly weather resistance adhesion is improved.
- the primer layer 3 excellent in adhesiveness is provided in this way, the hard-coat film excellent in weather resistance, such as the weather-proof adhesion concerning the hard-coat layer 4, and a weather cracking property, is obtained.
- the resin that is the material of the resin substrate used in the present invention includes polycarbonate resin, polystyrene resin, aromatic polyester resin, acrylic resin, polyester resin, polyarylate resin, and the weight of halogenated bisphenol A and ethylene glycol.
- examples thereof include thermoplastic resins such as condensates, acrylic urethane resins, and halogenated aryl group-containing acrylic polymers.
- polycarbonate resins such as aromatic polycarbonate resins and acrylic resins such as polymethyl methacrylate acrylic resins are preferable, and polycarbonate resins are more preferable.
- bisphenol A-based polycarbonate resins are particularly preferable.
- the resin substrate may contain two or more types of thermoplastic resins as described above, or may be a laminated substrate in which two or more layers are laminated using these resins.
- the shape of the resin substrate is not particularly limited, and may be a flat plate or curved.
- the color tone of the resin substrate is preferably colorless and transparent or colored and transparent.
- the resin substrate with a hard coat film of the present invention has a primer layer 3 mainly composed of an acrylic polymer (P) and a silyl group-containing acrylic polymer ( ⁇ ) on at least one surface of the resin substrate 2.
- the primer layer 3 is a layer provided to improve the adhesion between the resin substrate 2 and a hard coat layer 4 described later, and the adhesion between the resin substrate 2 and the resin substrate 2 is ensured by being in direct contact with the resin substrate 2.
- the primer layer 3 of the resin substrate with a hard coat film of the present invention contains, as main components, an acrylic polymer (P) and a silyl group-containing acrylic polymer ( ⁇ ) described below.
- the acrylic polymer (P) which is a main component constituting the primer layer a homopolymer or copolymer (copolymer) having a monomer having a methacrylic group (for example, methacrylic acid ester) as a polymerization unit is used.
- the acrylic polymer (P) is a homopolymer or copolymer having a polymerization unit of an alkyl methacrylate having 1 to 6 carbon atoms and having a polymerization unit of 90 based on methyl methacrylate. Those containing ⁇ 100 mol% are used.
- the acrylic polymer (P) may be a homopolymer having methyl methacrylate as a polymerization unit as long as it contains 90 to 100 mol% of a polymerization unit based on methyl methacrylate. Further, a copolymer having a polymerization unit of a methacrylic acid alkyl ester having an alkyl group having 2 to 6 carbon atoms may be used.
- acrylic polymer (P) used in the present invention examples include alkyl methacrylates having 1 to 6 carbon atoms in the alkyl group, especially methyl methacrylate, n-butyl methacrylate, tert-butyl methacrylate, and ethyl methacrylate.
- a homopolymer obtained by polymerizing one kind selected from isobutyl methacrylate and the like as a monomer, and a copolymer of these monomers are preferable.
- homopolymers such as methyl methacrylate, tert-butyl methacrylate, and ethyl methacrylate (that is, polymethyl methacrylate, polytert-butyl methacrylate, polyethyl methacrylate), or methyl methacrylate and n methacrylate -A copolymer with one or more selected from butyl, ethyl methacrylate and isobutyl methacrylate is more preferred.
- the acrylic polymer (P) preferably has a mass average molecular weight Mw of 20,000 or more, more preferably 50,000 or more, and preferably 1,500,000 or less.
- the acrylic polymer (P) having a mass average molecular weight Mw within this range is preferable because it exhibits sufficient adhesion and strength performance as a primer layer.
- the mass average molecular weight Mw refers to a value measured with polystyrene as a standard substance by gel permeation chromatography.
- acrylic polymer (P) is also commercially available.
- these commercially available products for example, Dianal LR269 (trade name, manufactured by Mitsubishi Rayon Co., Ltd., polymethyl methacrylate (PMMA), Mass average molecular weight: 100,000), LR248 (trade name, manufactured by Mitsubishi Rayon Co., Ltd., polymethyl methacrylate (PMMA), mass average molecular weight: 155,000), etc., commercially available as a solution previously dissolved in an appropriate solvent. Can be used.
- Dianal BR80 (trade name, manufactured by Mitsubishi Rayon Co., Ltd., polymethyl methacrylate (PMMA), mass average molecular weight: 90,000), Dianal BR88 (trade name, manufactured by Mitsubishi Rayon Co., Ltd., polymethyl methacrylate (PMMA))
- Acrylic compounds such as M-4003 (trade name, manufactured by Negami Kogyo Co., Ltd., polymethyl methacrylate (PMMA), mass average molecular weight: 700,000 to 1,300,000), etc.
- the polymer can be used by dissolving in a suitable solvent. Furthermore, it is also possible to use a mixture of two or more of these acrylic polymers.
- the toughness of the primer layer 3 can be increased and the impact resistance can be improved.
- the primer layer 3 contains a silyl group-containing acrylic polymer ( ⁇ ) together with the acrylic polymer (P) described above. That is, the primer layer of the present invention contains an acrylic polymer (P) and a silyl group-containing acrylic polymer ( ⁇ ) as main components.
- the primer layer mainly composed of the acrylic polymer (P) and the silyl group-containing acrylic polymer ( ⁇ ) is the sum of the acrylic polymer (P) and the silyl group-containing acrylic polymer ( ⁇ ) in the primer layer. It means that the content ratio of is 50% by mass or more.
- the silyl group-containing acrylic polymer ( ⁇ ) is a polymer based on polymer units having hydrolyzable silyl groups and / or SiOH groups (hereinafter sometimes referred to as silyl group-containing polymer units) ( ⁇ 1) and methyl methacrylate. Unit ( ⁇ 2).
- the number of hydrolyzable silyl groups contained in each silyl group-containing polymer unit ( ⁇ 1) is usually 1 but may be 2 or more.
- the silyl group-containing polymer unit ( ⁇ 1) is preferably one in which a hydrolyzable silyl group is bonded via a C—Si bond to a hydrocarbon group bonded to an acrylic polymer as a main chain.
- the silyl group-containing polymer unit ( ⁇ 1) is obtained by polymerization / copolymerization of an acrylic monomer (that is, a silyl group-containing acrylic monomer) in which a hydrolyzable silyl group is bonded via a C—Si bond. This can be obtained and can be a polymerized unit ( ⁇ 1) having a hydrolyzable silyl group and / or a SiOH group.
- the silyl group-containing acrylic polymer ( ⁇ ) is obtained by a reaction between hydrolyzable silyl groups and / or SiOH groups contained in the polymer, or hydrolyzable silyl groups and / or SiOH groups of the polymer. And a hydrolyzable silyl group and / or SiOH group of the organopolysiloxane constituting the hard coat layer described later is considered to form a siloxane bond.
- the primer layer contains a silyl group-containing acrylic polymer containing a polymer unit having a hydrolyzable silyl group and / or SiOH group
- the hydrolyzable silyl group and / or SiOH group is It shall be interpreted as including a case where a siloxane bond is formed.
- the silyl group-containing acrylic polymer ( ⁇ ) does not contain a polymer unit having an aromatic hydrocarbon group in the side chain. That is, it does not have a structure in which a monomer having an aromatic hydrocarbon group such as an ultraviolet absorbing group is copolymerized.
- the acrylic polymer (P) and the silyl group-containing acrylic polymer ( ⁇ ) are in a mass ratio, that is, (content of acrylic polymer (P)) / (acrylic polymer (P ) And the content of the silyl group-containing acrylic polymer ( ⁇ )) ⁇ 100 so that the value is 50 to 98% by mass.
- the value of (acrylic polymer (P) content) / (total amount of acrylic polymer (P) content and silyl group-containing acrylic polymer ( ⁇ ) content) ⁇ 100 is obtained. If it is less than 50% by mass, the toughness of the primer layer 3 is lowered, and cracks or the like may easily occur in the primer layer 3.
- the value of (content of acrylic polymer (P)) / (total content of acrylic polymer (P) and content of silyl group-containing acrylic polymer ( ⁇ )) ⁇ 100 is 98% by mass.
- siloxane bonds (—O—Si—O—) are not sufficiently formed between the primer layer 3 and the hard coat layer 4, and it is difficult to sufficiently improve the adhesion with the hard coat layer 3. There is a risk of becoming.
- silyl group-containing acrylic polymer ( ⁇ ) Such a silyl group-containing acrylic polymer ( ⁇ ) may be referred to as (A) an acrylic monomer having a hydrolyzable silyl group bonded via a C—Si bond (hereinafter referred to as a silyl group-containing acrylic monomer). ) And (B) methyl methacrylate can be copolymerized.
- silyl group-containing acrylic monomer As the silyl group-containing acrylic monomer (A), one molecule has a hydrolyzable silyl group bonded via one or more C—Si bonds, and one acrylic group or Any monomer having a methacryl group can be used without any particular limitation. In particular, a methacrylic acid ester having one hydrolyzable silyl group is preferable.
- the hydrolyzable silyl group is a group in which the hydrolyzable group is directly bonded to the silicon atom, and the hydrogen atom of the silyl group (—SiH 3 ) is substituted with the hydrolyzable group.
- the hydrolyzable group is a group that becomes a hydroxyl group (OH group bonded to a silicon atom) by hydrolysis, and specifically includes a methoxy group, an ethoxy group, a propoxy group, and an isopropoxy group.
- Alkoxy groups such as a methoxy group and an ethoxy group are preferred because of easy controllability of hydrolyzability and availability.
- substituent other than the hydrolyzable group examples include an alkyl group such as a methyl group, an ethyl group, a propyl group, a hexyl group, and a decyl group, and a phenyl group. From the standpoint of availability, it is preferable to use a substituent other than the hydrolyzable group that is a methyl group or an ethyl group.
- silyl group-containing acrylic monomer to which such a hydrolyzable silyl group is bonded examples include, for example, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyldimethylmethoxysilane, Examples include 3-methacryloxypropyltriethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-acryloxypropyltrimethoxysilane, and 3-acryloxypropylmethyldimethoxysilane. Among these, 3-methacryloxypropyltrimethoxysilane and 3-methacryloxypropylmethyldimethoxysilane are particularly preferable from the viewpoints of availability, handling, crosslinking density, and reactivity.
- the content ratio of the polymer unit ( ⁇ 2) based on methyl methacrylate (MMA) in the silyl group-containing acrylic polymer ( ⁇ ) is 50 to 95 mol of the entire polymer units constituting the silyl group-containing acrylic polymer ( ⁇ ). %.
- the polymerization unit based on methyl methacrylate (MMA) is less than 50 mol%, the compatibility between the silyl group-containing acrylic polymer ( ⁇ ) and the acrylic polymer (P) which is the main component of the primer layer is low. There is a fear.
- the content ratio of the polymerization unit ( ⁇ 1) having a hydrolyzable silyl group and / or SiOH group may be 5 mol% or more and 50 mol% or less of the entire polymerization unit constituting the silyl group-containing acrylic polymer ( ⁇ ). preferable.
- the hydrolyzable silyl group of this polymerized unit and the terminal of the organopolysiloxane constituting the hard coat layer described later Reaction with a group (for example, Si—OX group, where —OX represents a hydroxyl group or an alkoxy group) does not sufficiently occur, and the effect of improving the adhesion with the hard coat layer cannot be sufficiently obtained.
- the copolymer composition in the silyl group-containing acrylic polymer ( ⁇ ) is such that (A) the polymer unit ( ⁇ 1) having a hydrolyzable silyl group and / or SiOH group is 5 to 50 mol%, and (B) methyl methacrylate.
- the polymerization unit ( ⁇ 2) based on (MMA) is preferably 50 to 95 mol%.
- Particularly preferred copolymer composition is (A) 5-40 mol% of polymerized units ( ⁇ 1) having hydrolyzable silyl groups and / or SiOH groups, and (B) polymerized units based on methyl methacrylate (MMA) ( ⁇ 2). Is 60 to 95 mol%.
- the silyl group-containing acrylic polymer ( ⁇ ) is a polymer unit having a polymer unit ( ⁇ 2) based on methyl methacrylate (MMA) and a hydrolyzable silyl group and / or SiOH group, that is, a silyl group-containing polymer unit ( ⁇ 1).
- the silyl group-containing acrylic polymer ( ⁇ ) the molar ratio of (polymer unit based on MMA ( ⁇ 2)) :( silyl group-containing polymer unit ( ⁇ 1)), ie, (polymer unit based on MMA ( ⁇ 2)) / (silyl If the value of the group-containing polymerization unit ( ⁇ 1) is less than 50/50, the compatibility between the silyl group-containing acrylic polymer ( ⁇ ) and the acrylic polymer (P) in the primer layer may be low. There is. Moreover, since unreacted hydrolyzable groups are likely to remain, post-crosslinking with time may be formed, and cracks may be easily generated.
- the molar ratio of the polymer unit ( ⁇ 2) based on methyl methacrylate (MMA) and the polymer unit ( ⁇ 1) having a hydrolyzable silyl group and / or SiOH group is more preferably 60:40 to 90:10. It is preferable.
- the silyl group-containing acrylic polymer ( ⁇ ) can be synthesized by a known method.
- a peroxide such as dicumyl peroxide or benzoyl peroxide or 2,2′-azobis (isobutyro) It is obtained by adding an initiator for radical polymerization selected from azo compounds such as nitrile) and reacting under heating (40 to 150 ° C., particularly 50 to 120 ° C. for 1 to 10 hours, particularly 3 to 8 hours).
- an initiator for radical polymerization selected from azo compounds such as nitrile
- X and Y represent the molar ratio of (B) polymerized units based on methyl methacrylate (MMA) and (A) polymerized units based on 3-methacryloxypropyltrimethoxysilane, respectively.
- MMA methyl methacrylate
- X + Y 100.
- the molar ratio X of polymer units based on (B) methyl methacrylate (MMA) is preferably 50 to 95 as described above.
- the molar ratio Y of polymerized units based on (A) 3-methacryloxypropyltrimethoxysilane is preferably 5-50.
- the mass average molecular weight Mw of the silyl group-containing acrylic polymer ( ⁇ ) is preferably 5,000 to 300,000.
- Mw The mass average molecular weight of the silyl group-containing acrylic polymer
- ⁇ exceeds 300,000, the viscosity of the polymer becomes excessively high and it becomes difficult to apply a primer layer forming composition (described later) containing the polymer. In some cases, an appropriate film thickness cannot be obtained in the primer layer 3.
- the mass average molecular weight of the silyl group-containing acrylic polymer ( ⁇ ) is less than 5,000, the entanglement with the acrylic polymer in the primer layer becomes weak, and the strength of the primer layer 3 may be reduced. .
- these silyl group-containing acrylic polymers ( ⁇ ) do not contain polymerized units having an aromatic hydrocarbon group in the side chain. That is, it does not have a structure in which a monomer having an aromatic hydrocarbon group such as an ultraviolet absorbing group is copolymerized.
- the silyl group-containing acrylic polymer ( ⁇ ) contained in the primer layer has a structure in which a monomer having an aromatic hydrocarbon group such as an organic ultraviolet absorbing group is copolymerized, the organo constituting the hard coat layer The reactivity with polysiloxane becomes insufficient, and improvement in adhesion, particularly weather resistance adhesion, cannot be expected.
- the familiarity with the acrylic polymer (P) which is the main component of the primer layer is insufficient, and the scratch resistance of the hard coat film cannot be sufficiently improved.
- the silyl group-containing acrylic polymer ( ⁇ ) preferably does not contain a polymer unit having a hydroxyalkyl group.
- the silyl group-containing acrylic polymer ( ⁇ ) contained in the primer layer free of hydroxyalkyl groups that are hydrophilic groups, the silyl group-containing acrylic polymer ( ⁇ ) has low hygroscopicity and deteriorates moisture resistance.
- the primer layer can be suppressed.
- the primer layer preferably contains an ultraviolet absorber in order to suppress yellowing of the resin substrate.
- an ultraviolet absorber the thing similar to the ultraviolet absorber contained in the composition for hard-coat layer formation mentioned later can be used. These may use 1 type and may use 2 or more types together.
- the content of the ultraviolet absorber in the primer layer is preferably 1 to 50 parts by mass with respect to 100 parts by mass of the resin component such as the acrylic polymer (P) and the silyl group-containing acrylic polymer ( ⁇ ). ⁇ 30 parts by weight is particularly preferred.
- the primer layer may further contain a light stabilizer and the like.
- the light stabilizer include hindered amines; nickel complexes such as nickel bis (octylphenyl) sulfide, nickel complex-3,5-di-tert-butyl-4-hydroxybenzyl phosphate monoethylate, nickel dibutyldithiocarbamate. Two or more of these may be used in combination.
- the content of the light stabilizer in the primer layer is preferably 0.01 to 50 parts by mass with respect to 100 parts by mass of the resin component such as the acrylic polymer (P) and the silyl group-containing acrylic polymer ( ⁇ ). 0.1 to 10 parts by mass is particularly preferable.
- the method for forming the primer layer on at least one surface of the resin substrate is not particularly limited, but preferably the acrylic polymer (P) and the silyl group-containing acrylic.
- a method is used in which a primer layer forming composition containing a polymer ( ⁇ ), an ultraviolet absorber, and a solvent is applied onto a resin substrate and dried.
- the primer layer forming composition used for forming the primer layer usually contains a solvent.
- the solvent is not particularly limited as long as it is a solvent capable of stably dissolving the acrylic polymer (P). Specifically, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone; ethers such as tetrahydrofuran, 1,4-dioxane and 1,2-dimethoxyethane; esters such as ethyl acetate, butyl acetate and methoxyethyl acetate Methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, 2-methyl-1-propanol, 2-methoxyethanol, 2-butoxyethanol, 1-methoxy-2-propanol, diacetone Alcohols such as alcohol; hydrocarbons such as n-hexane, n-heptane, isoctane,
- the amount of the solvent is preferably 50 to 10,000 parts by mass, particularly preferably 100 to 10,000 parts by mass with respect to 100 parts by mass of the resin component such as acrylic polymer (P).
- the content of the nonvolatile component (solid content) in the primer layer forming composition is preferably 0.5 to 75% by mass, particularly 1 to 60% by mass, based on the total amount of the composition. preferable.
- the primer layer forming composition may further contain additives such as a leveling agent, an antifoaming agent and a viscosity modifier.
- the method for applying the primer layer forming composition on the resin substrate is not particularly limited, and examples thereof include spray coating, dip coating, flow coating, spin coating, and die coating.
- the heating conditions for drying are not particularly limited, but are preferably 50 to 140 ° C. and 5 minutes to 3 hours.
- the primer layer formed on the resin substrate using the above primer layer forming composition cannot prevent yellowing due to weathering deterioration of the resin substrate itself if the thickness of the primer layer is too thin.
- the yellowing of the substrate, weathering cracks, and weather adhesion are reduced, and as a result, the weather resistance of the resin substrate with a hard coat film is lowered.
- the thickness of such a primer layer is preferably 0.1 ⁇ m or more and 7 ⁇ m or less, and particularly preferably 2 ⁇ m or more and 5 ⁇ m or less.
- this film thickness means the thickness when a primer layer is formed alone on a substrate such as a resin substrate.
- the hard coat layer used in the resin substrate with a hard coat film of the present invention contains a cured product of organopolysiloxane as a main component.
- the polyorganosiloxane that forms the cured product may be a curable polyorganosiloxane. For example, it can be used without particular limitation.
- Organopolysiloxane is composed of silicon-containing bond units called M units, D units, T units, and Q units.
- the curable organopolysiloxane is an oligomeric polymer mainly composed of T units or Q units, a polymer composed only of T units, a polymer composed only of Q units, T units and Q units.
- polymers composed of units may further contain a small amount of M units and D units.
- the T unit has one silicon atom, one hydrogen atom or monovalent organic group bonded to the silicon atom, and an oxygen atom bonded to another silicon atom ( Or a unit having three functional groups capable of bonding to other silicon atoms).
- the monovalent organic group bonded to the silicon atom is a monovalent organic group in which the atom bonded to the silicon atom is a carbon atom.
- the functional group that can be bonded to another silicon atom is a hydroxyl group or a group that becomes a hydroxyl group by hydrolysis (hereinafter referred to as a hydrolyzable group).
- the total number of oxygen atoms bonded to other silicon atoms and functional groups that can bond to other silicon atoms is three, and the number of functional groups that can bond to oxygen atoms bonded to other silicon atoms and other silicon atoms is different.
- the T unit is classified into three types of units called T1, T2, and T3.
- T1 has one oxygen atom bonded to another silicon atom
- T2 has two oxygen atoms
- T3 has three oxygen atoms.
- an oxygen atom bonded to another silicon atom is represented by O *
- a monovalent functional group that can be bonded to another silicon atom is represented by Z.
- O * representing an oxygen atom bonded to another silicon atom is an oxygen atom bonded between two silicon atoms, and is an oxygen atom in a bond represented by Si—O—Si. Accordingly, one O * exists between the silicon atoms of two silicon-containing bond units. In other words, O * represents an oxygen atom shared by two silicon atoms of two silicon-containing bond units. In the chemical formula of the silicon-containing bond unit described later, it is expressed as if O * is bonded to one silicon atom, but this O * is an oxygen atom shared with the silicon atom of other silicon-containing bond units. Yes, it does not mean that two silicon-containing bond units are bonded by a bond represented by Si—O * —O * —Si.
- the M unit is a unit having 3 organic groups and O * 1
- the D unit is a unit having 2 organic groups and O * 2 (or O * 1 and 1 Z group)
- Q The unit is a unit having 0 organic group and 0 * 4 organic groups (or a total of 4 O * 1 to 3 and 3 to 1 Z groups).
- Each silicon-containing bond unit is formed from a compound (hereinafter also referred to as a monomer) having only a Z group that does not have an oxygen atom (O *) bonded to another silicon atom.
- the monomer forming the T unit is hereinafter referred to as T monomer.
- Monomers that form M units, D units, and Q units are also referred to as M monomers, D monomers, and Q monomers.
- This monomer is represented by (R′—) a Si (—Z) 4-a .
- a represents an integer of 0 to 3
- R ′ represents a hydrogen atom or a monovalent organic group
- Z represents a monovalent functional group capable of bonding to a hydroxyl group or another silicon atom.
- the Z group is usually a hydrolyzable group.
- R ′ is preferably in the same category as R described later.
- the curable organopolysiloxane is obtained by a reaction in which a part of the Z group of the monomer is converted to O *.
- the organopolysiloxane is a copolymer comprising two or more silicon-containing bond units, these copolymers are usually obtained from a mixture of the corresponding monomers.
- the Z group of the monomer is a hydrolyzable group, the Z group is converted into a hydroxyl group by a hydrolysis reaction, and then two silicon atoms are converted by a dehydration condensation reaction between two hydroxyl groups bonded to separate silicon atoms. Bonding through an oxygen atom (O *).
- hydroxyl groups (or Z groups that have not been hydrolyzed) remain, and when the curable organopolysiloxane is cured, these hydroxyl groups and Z groups react and cure as described above.
- the cured product of the curable organopolysiloxane is a three-dimensionally crosslinked polymer, and the cured product of the curable organopolysiloxane having many T units and Q units is a cured product having a high crosslinking density.
- the Z group of the curable organopolysiloxane is converted to O *, but a part of the Z group (particularly hydroxyl group) remains and is considered to be a cured product having a hydroxyl group.
- the curable organopolysiloxane is cured at a high temperature, a cured product in which almost no hydroxyl groups remain may be obtained.
- the Z group of the monomer is a hydrolyzable group
- examples of the Z group include an alkoxy group, a chlorine atom, an acyloxy group, and an isocyanate group.
- a monomer in which the Z group is an alkoxy group is used as the monomer.
- the alkoxy group is a hydrolyzable group having a relatively low reactivity as compared with a chlorine atom and the like, and in the curable organopolysiloxane obtained by using a monomer in which the Z group is an alkoxy group, the Z group is not present together with the hydroxyl group. Often an alkoxy group of the reaction is present.
- the Z group of the monomer is a hydrolyzable group having a relatively high reactivity (for example, a chlorine atom)
- most of the Z groups in the curable organopolysiloxane obtained using the monomer are hydroxyl groups. Therefore, in a normal curable organopolysiloxane, the Z group in each unit constituting it is often composed of a hydroxyl group or a hydroxyl group and an alkoxy group.
- curable organopolysiloxanes having T units as main silicon-containing bond units are preferably used.
- curable organopolysiloxane is simply referred to as organopolysiloxane.
- organopolysiloxane (T) refers to an M unit, a D unit, a T unit, and An organopolysiloxane in which the ratio of the number of T units to the total number of Q units is from 50 to 100%.
- an organopolysiloxane having a ratio of the number of T units of from 70 to 100% is particularly preferred. Uses an organopolysiloxane having a T-unit ratio of 90 to 100%. Further, as other units contained in a small amount other than T units, D units and Q units are preferable, and Q units are particularly preferable.
- the ratio of the number of M units, D units, T units, and Q units in the organopolysiloxane can be calculated from the value of the peak area ratio by 29 Si-NMR.
- the organopolysiloxane (T) preferably used in the present invention is an organopolysiloxane having T units represented by the following T1 to T3.
- T1 R—Si (—OX) 2 (—O * —)
- T2 R—Si (—OX) (— O * —) 2
- T3 R—Si (—O *-) 3 (Wherein R represents a hydrogen atom or a substituted or unsubstituted monovalent organic group having 1 to 10 carbon atoms, X represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and O * represents Represents an oxygen atom connecting two silicon atoms.)
- R in the above chemical formula is not limited to one type, and T1, T2, and T3 may each include a plurality of types of R.
- —OX in the above chemical formula represents a hydroxyl group or an alkoxy group.
- -OX may be the same or different between T1 and T2.
- the two —OX in T1 may be different.
- one may be a hydroxyl group and the other may be an alkoxy group.
- the alkoxy groups may be different alkoxy groups. However, as described later, usually, the two alkoxy groups are the same alkoxy group.
- T0 a T unit that does not have an oxygen atom (O *) that bonds two silicon atoms and has only three -OX is hereinafter referred to as T0.
- T0 actually corresponds to an unreacted T monomer contained in the organopolysiloxane and is not a silicon-containing bond unit. This T0 is measured in the same manner as T1 to T3 in the analysis of units of T1 to T3.
- T0 to T3 in the organopolysiloxane can be analyzed by measuring the bonding state of silicon atoms in the organopolysiloxane by nuclear magnetic resonance analysis ( 29 Si-NMR). The ratio of the number of T0 to T3 is determined from the peak area ratio of 29 Si-NMR. -OX in the organopolysiloxane molecule can be analyzed by infrared absorption analysis. The ratio of the number of hydroxyl groups bonded to silicon atoms and the number of alkoxy groups is determined from the peak area ratio of the infrared absorption peaks of the two.
- the weight average molecular weight Mw, the number average molecular weight Mn, and the dispersity Mw / Mn of the organopolysiloxane are values measured by gel permeation chromatography using polystyrene as a standard substance.
- the characteristics of such an organopolysiloxane do not refer to the characteristics of one molecule but are determined as the average characteristics of each molecule.
- T two or more different T1, T2, and T3 may exist in each molecule.
- two or more types of T2 with different R may exist.
- Such organopolysiloxanes are obtained from a mixture of two or more T monomers.
- an organopolysiloxane obtained from a mixture of two or more T monomers having different R it is considered that two or more T1, T2, and T3 having different R exist.
- the ratio of the number of different R in the organopolysiloxane obtained from a mixture of a plurality of T monomers having different R reflects the composition ratio of the T monomer mixture having different R as a whole T unit.
- the ratio of the number of units with different R in each of T1, T2, and T3 does not necessarily reflect the composition ratio of T monomer mixtures with different R. This is because the reactivity of the T monomer, T1, and T2 may differ depending on the difference in R even if the three —OXs in the T monomer are the same.
- the organopolysiloxane (T) is preferably produced from at least one T monomer represented by R—Si (—OY) 3 .
- R is the same as R described above, and Y represents an alkyl group having 1 to 6 carbon atoms.
- Y may be a substituted alkyl group such as an alkoxy-substituted alkyl group in addition to an unsubstituted alkyl group.
- Three Y in one molecule may be different. However, usually three Y are the same alkyl group.
- Y is preferably an alkyl group having 1 to 4 carbon atoms, and more preferably 1 or 2 carbon atoms. Specific examples of Y include a methyl group, an ethyl group, an n-propyl group, an n-butyl group, a t-butyl group, and a 2-methoxyethyl group.
- R is a hydrogen atom or a substituted or unsubstituted monovalent organic group having 1 to 10 carbon atoms.
- the organic group means an organic group in which the atom bonded to the silicon atom is a carbon atom as described above.
- Examples of the unsubstituted monovalent organic group include hydrocarbon groups such as an alkyl group, an alkenyl group, an alkynyl group, a cycloalkyl group, an aryl group, and an aralkyl group. These hydrocarbon groups include alkyl groups having 1 to 10 carbon atoms, alkenyl groups and alkynyl groups having 2 to 10 carbon atoms, cycloalkyl groups having 5 or 6 carbon atoms, aryl groups having 6 to 10 carbon atoms, and 7 carbon atoms. ⁇ 10 aralkyl groups are preferred.
- Examples of the substituted monovalent organic group include a hydrocarbon group in which a ring hydrogen atom such as a cycloalkyl group, an aryl group, and an aralkyl group is substituted with an alkyl group, and the hydrogen atom of the hydrocarbon group is a halogen atom or a functional group And a substituted organic group substituted with a functional group-containing organic group.
- a hydroxyl group, mercapto group, carboxyl group, epoxy group, amino group, cyano group and the like are preferable.
- an alkyl group having a chlorine atom or a fluorine atom such as a chloroalkyl group or a polyfluoroalkyl group is preferable.
- the functional group-containing organic group include an alkoxy group, an acyl group, an acyloxy group, an alkoxycarbonyl group, a glycidyl group, an epoxycyclohexyl group, an alkylamino group, a dialkylamino group, an arylamino group, and an N-aminoalkyl-substituted aminoalkyl group. preferable.
- the T monomer having a substituted organic group substituted with a functional group or a functional group-containing organic group includes a category of compounds called silane coupling agents.
- substituted organic group examples include the following organic groups. 3-chloropropyl group, 3,3,3-trifluoropropyl group, 3-mercaptopropyl group, p-mercaptomethylphenylethyl group, 3-acryloyloxypropyl group, 3-methacryloyloxypropyl group, 3-glycidoxy Propyl group, 2- (3,4-epoxycyclohexyl) ethyl group, 3-aminopropyl group, N-phenyl-3-aminopropyl group, N- (2-aminoethyl) -3-aminopropyl group, 2-cyanoethyl Group.
- a particularly preferred monovalent organic group as R is an alkyl group having 1 to 4 carbon atoms.
- the organopolysiloxane (T) is preferably an organopolysiloxane obtained by using a T monomer having an alkyl group having 1 to 4 carbon atoms alone or two or more thereof. Further, as the organopolysiloxane (T), an organopolysiloxane obtained by using one or more T monomers having an alkyl group having 1 to 4 carbon atoms and a small amount of other T monomers is also preferable.
- the proportion of other T monomers is preferably 30 mol% or less, particularly preferably 15 mol% or less, based on the total amount of T monomers.
- a T monomer having a substituted organic group substituted with a functional group, a functional group-containing organic group, or the like in a category called a silane coupling agent is preferable.
- T monomer having an alkyl group having 1 to 4 carbon atoms include, for example, methyltrimethoxysilane, methyltriethoxysilane, methyltripropoxysilane, ethyltrimethoxysilane, and ethyltriethoxysilane. In particular, methyltrimethoxysilane and ethyltrimethoxysilane are preferable.
- T monomer having a substituted organic group and the like include the following compounds.
- R-Si (-OY) other than T monomer represented by 3 (R'-) a Si (-Z ) T monomers represented by 4-a (a 3) , for example, methyltrichlorosilane, Examples thereof include ethyltrichlorosilane, phenyltrichlorosilane, 3-glycidoxypropyltrichlorosilane, methyltriacetoxysilane, and ethyltriacetoxysilane.
- the Z group is preferably an alkoxy group having 1 to 4 carbon atoms, an acetoxy group, or the like. Examples of the D monomer include the following compounds.
- the four Z groups may be different but are usually the same.
- the Z group is preferably an alkoxy group having 1 to 4 carbon atoms, and particularly preferably a methoxy group or an ethoxy group.
- Examples of the Q monomer include the following compounds.
- the organopolysiloxane (T) used in the present invention is obtained by subjecting the above T monomer and the like to partial hydrolysis condensation. Usually, this reaction is performed by heating T monomer or the like and water in a solvent. A catalyst is preferably present in the reaction system.
- the desired organopolysiloxane can be produced by adjusting the reaction conditions such as the type of monomer, the amount of water, the heating temperature, the type and amount of catalyst, and the reaction time. In some cases, a commercially available organopolysiloxane can be used as it is as the target organopolysiloxane, or the desired organopolysiloxane can be produced using a commercially available organopolysiloxane.
- Acid catalysts include inorganic acids such as hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, nitrous acid, perchloric acid, sulfamic acid; formic acid, acetic acid, propionic acid, butyric acid, oxalic acid, succinic acid, maleic acid, lactic acid, p- An organic acid such as toluenesulfonic acid may be mentioned. In particular, acetic acid is preferred.
- the solvent is preferably a hydrophilic organic solvent, and particularly preferably an alcohol solvent.
- alcohol solvents examples include methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, 2-methyl-1-propanol, 2-ethoxyethanol, diacetone alcohol, 2-butoxyethanol and the like. It is done.
- the reaction temperature can be reacted at room temperature when a catalyst is present. Usually, an appropriate temperature is adopted from the reaction temperature of 20 to 80 ° C. according to the purpose.
- the hydrolysis condensation reaction is a reaction in which T1 is generated from T0 (T monomer), T2 is generated from T1 and T3 is generated from T2.
- Condensation reaction in which at least one hydrolyzable group is converted to a hydroxyl group from T0 to T1
- the reaction rate of the condensation reaction in which T3 is generated from the reaction becomes slower in this order. Even considering the hydrolysis reaction of the hydrolyzable group, the peak of the abundance of each unit is considered to move from T0 to T3 as the reaction proceeds.
- the reaction conditions are relatively mild, the movement of the abundance peak is considered to proceed relatively orderly.
- the organopolysiloxanes (T) used in the present invention the organopolysiloxane (a) has a relatively high molecular weight in which the amount of T0 and T1 is small and the ratio of the amounts of T2 and T3 is in a specific range.
- Organopolysiloxanes, and such organopolysiloxanes can be produced by selecting relatively mild reaction conditions.
- the reactivity of the condensation reaction varies depending on R, and when R is different, the reactivity of the hydroxyl group also varies.
- R for example, when R is an alkyl group, the smaller the number of carbon atoms in the alkyl group), the higher the reactivity of the hydroxyl group. Accordingly, it is preferable to select the T monomer in consideration of the relationship between the reactivity of the hydrolyzable group and the reactivity of the hydroxyl group.
- the rate of hydrolysis reaction of a hydrolyzable group to a hydroxyl group varies depending on the type of hydrolyzable group, and it is preferable to consider the relationship with the rate of condensation reaction. For example, when the OX group of T2 is an alkoxy group, if the rate of the hydrolysis reaction is too slow, T2 in which the OX group is a hydroxyl group decreases. Similarly, when the hydrolysis reaction rate is too slow, T1 in which the OX group is a hydroxyl group decreases. For this reason, it becomes difficult to obtain a high ratio of the amount of hydroxyl groups to alkoxy groups in the organopolysiloxane.
- the alkoxy group which is an OX group is preferably a highly reactive alkoxy group, that is, an alkoxy group having a low carbon number, and most preferably a methoxy group.
- the reactivity of the hydrolyzable group is sufficiently high, an organopolysiloxane having a high proportion of hydroxyl groups can be obtained from an organopolysiloxane having a high proportion of hydrolyzable groups without much progress of the condensation reaction.
- one kind of curable organopolysiloxane (T) thus obtained may be blended alone, or two or more kinds may be blended together. Is also possible.
- a composition hereinafter referred to as “hard coat” that is usually used and contains a material before curing of the components constituting the hard coat layer.
- a composition for forming a layer " is prepared and used.
- the curable organopolysiloxane (T) preferably used in the present invention is also incorporated into such a hard coat layer-forming composition in the production process so as to be contained as a cured product in the obtained hard coat layer. It becomes possible.
- organopolysiloxane (a) and organopolysiloxane (b) will be described below as a particularly preferred combination of organopolysiloxane (T) from the viewpoint of scratch resistance.
- the curable organopolysiloxane used in the present invention is described below. It is not limited to these. Further, the organopolysiloxane (a) and the organopolysiloxane (b) are not precluded from being used in the present invention alone as the organopolysiloxane (T).
- the ratio of the number (A) that is an alkoxy group to the number (B) that is a hydroxyl group, that is, (B) / (A) is the molecular average. It is 12.0 or more.
- the organopolysiloxane (a) has a mass average molecular weight of 800 to 8000.
- the organopolysiloxane (a) does not substantially contain T0 which is a T monomer.
- (T2 + T3) / (T1 + T2 + T3) is preferably in the range of 0.85 to 1.00, 0.90 or more More preferably, it is less than 1.00.
- the preferred range is 2.0 to 4.0.
- the organopolysiloxane (a) and the organopolysiloxane (b) described later can be obtained.
- the scratch resistance of the finally obtained hard coat layer can be improved.
- the above (B) / (A) in the organopolysiloxane (a) is a parameter indicating condensation reactivity.
- alkoxy groups left unreacted during the formation of the cured film may cause a decrease in scratch resistance of the finally obtained hard coat layer, and if post-curing progresses, it may cause micro cracks.
- (B) / (A) in the organopolysiloxane (a) is 12.0 or more, preferably 16.0 or more. Note that (A) may be zero.
- the mass average molecular weight of the organopolysiloxane (a) is 800 to 8000, preferably 1000 to 6000.
- the organopolysiloxane (a) and the organopolysiloxane (b) are used in combination in the composition for forming a hard coat layer of the present invention.
- the scratch resistance of the finally obtained hard coat layer can be sufficiently improved.
- the organopolysiloxane (a) used in the hard coat layer forming composition for forming a hard coat layer having particularly excellent scratch resistance all T It is preferable that 70% by mass or more of the monomer is methyltrialkoxysilane, and preferably the alkoxy group has 1 to 4 carbon atoms. However, a small amount of T monomer other than methyltrialkoxysilane can be used in combination for the purpose of improving the adhesion, hydrophilicity, water repellency and the like.
- a T monomer or the like is subjected to a hydrolysis condensation reaction in a solvent in the presence of an acid catalyst.
- the water required for hydrolysis is usually 1 to 10 equivalents, preferably 1.5 to 7 equivalents, and more preferably 3 to 5 equivalents of water with respect to 1 equivalent of the monomer.
- the monomer is hydrolyzed and condensed, it can also be carried out in a reaction system in which colloidal silica is present as described later.
- colloidal silica colloidal silica
- water is supplied from this dispersion. Is done.
- the amount of the acid catalyst used is preferably from 0.1 to 50 parts by weight, particularly preferably from 1 to 20 parts by weight, based on 100 parts by weight of the monomer.
- the solvent the alcohol solvent is preferable, and methanol, ethanol, 2-propanol, 1-butanol, and 2-butanol are particularly preferable from the viewpoint of good solubility of the resulting organopolysiloxane (a). preferable.
- the reaction temperature is 20 to 40 ° C., and the reaction time is 1 hour to several days.
- the hydrolysis and condensation reaction of the monomer is an exothermic reaction, it is preferable that the temperature of the system does not exceed 60 ° C. It is also preferable to allow the hydrolysis reaction to proceed sufficiently under such conditions, and then to proceed the condensation reaction at 40 to 80 ° C. for 1 hour to several days in order to stabilize the resulting organopolysiloxane.
- Organopolysiloxane (a) can also be produced from commercially available organopolysiloxane. Since the commercially available organopolysiloxane is usually an organopolysiloxane having a higher proportion of alkoxy groups than the hydroxyl group, it is particularly similar to the desired organopolysiloxane (a) except for the above (B) / (A). It is preferable to produce the organopolysiloxane (a) by using the commercially available organopolysiloxane and increasing the proportion of hydroxyl groups by hydrolysis reaction.
- organopolysiloxane examples include the following organopolysiloxanes, which are partially hydrolyzed condensates of methyltrimethoxysilane. It should be noted that “ND” is not more than a detected amount when the 29 Si-NMR peak area ratio is measured using a nuclear magnetic resonance analyzer, manufactured by JEOL Ltd., ECP400 (trade name). Shown (the same applies below).
- the organopolysiloxane (a) When producing the organopolysiloxane (a) from the above-mentioned commercially available organopolysiloxane, it is preferable to hydrolyze the alkoxy group of the commercially available organopolysiloxane mainly in the presence of an acid catalyst. For example, 0 to 10 times (mass basis) of a solvent is added to a commercially available organopolysiloxane, stirred well, then an acid aqueous solution having a concentration of about 0.1 to 70% by mass is added, A method such as stirring at a temperature of 20 to 70 ° C. for 1 to 24 hours is preferable.
- a solvent to be used an aqueous solvent can be used, and the alcohol solvent to which water is added can also be used.
- organopolysiloxane (b) used in combination with the organopolysiloxane (a) in the composition for forming a hard coat layer used in the present invention is 1/10 to 1/1 of the mass average molecular weight of the organopolysiloxane (a). It is an organopolysiloxane having a mass average molecular weight of 5 times.
- the organopolysiloxane (b) is an organopolysiloxane having a mass average molecular weight smaller than that of the combined organopolysiloxane (a), and has the T1 to T3 units.
- the ratio of the numbers of T1, T2, and T3, the ratio of T3 / T2, and the ratio of (B) / (A) are not particularly limited.
- the mass average molecular weight of the organopolysiloxane (b) is preferably 1/8 to 1 / 1.5 times that of the combined organopolysiloxane (a).
- the weight average molecular weight of the organopolysiloxane (b) exceeds 1 / 1.5 times the weight average molecular weight of the organopolysiloxane (a), in other words, the weight average molecular weight of the organopolysiloxane (a)
- the mass average molecular weight of b) is less than 1.5 times, the toughness of the finally obtained hard coat layer is lowered, which causes cracks.
- the mass average molecular weight of the organopolysiloxane (b) is less than 1/10 times the mass average molecular weight of the organopolysiloxane (a), in other words, the mass average molecular weight of the organopolysiloxane (a) is the organopolysiloxane (b).
- the weight average molecular weight of 10 exceeds 10 times, the scratch resistance of the finally obtained hard coat layer is lowered, and there is a possibility that a hard coat layer having sufficient scratch resistance cannot be obtained.
- a large ratio of T0 and T1 in the organopolysiloxane (b) generally indicates that the hydrolysis reaction or condensation reaction of the raw material monomer was insufficient when the organopolysiloxane was produced.
- the composition for forming a hard coat layer containing this and the organopolysiloxane (a) is used for heat curing when forming a cured film.
- the occurrence of cracks tends to increase.
- the ratio of T3 of the resulting organopolysiloxane increases.
- the composition for forming a hard coat layer containing this and the organopolysiloxane (a) is used, and at the time of thermosetting when forming a cured film, Since appropriate crosslinking reaction becomes difficult, a cured film may not be formed, and a hard coat layer having sufficient scratch resistance may not be finally obtained.
- the organopolysiloxane (b) can be produced from a T monomer or the like in the same manner as the organopolysiloxane (a).
- Commercially available organopolysiloxane can be used as organopolysiloxane (b) as it is.
- Examples of commercially available organopolysiloxanes that can be used as the organopolysiloxane (b) include the following organopolysiloxanes.
- the notation of “trace” is 0.01 or more and 0.00 when the peak area ratio of 29 Si-NMR is measured using a nuclear magnetic resonance analyzer, manufactured by JEOL Ltd., ECP400 (trade name). It indicates that it is 25 or less (the same applies hereinafter).
- T0: T1: T2: T3 ND: 2: 36: 62.
- T0: T1: T2: T3 trace: 21: 58: 21.
- the ratio of the content of the organopolysiloxane (b) to the organopolysiloxane (a) is 1.5 to It is preferably 30 times, and more preferably 2 to 15 times.
- the organopolysiloxane three-dimensional crosslinked structure formed by the curing reaction is an organopolysiloxane (b) -based three-dimensional crosslinked.
- the component (a) organopolysiloxane is partially incorporated, and the finally obtained hard coat layer can have good scratch resistance.
- the hard coat layer forming composition used in the present invention contains the above curable organopolysiloxane, preferably organopolysiloxane (T).
- the content of the organopolysiloxane in the composition for forming a hard coat layer is preferably 50 to 100% by mass with respect to the total amount of the composition excluding the solvent (hereinafter referred to as “nonvolatile component” as necessary) More preferably, it is 60 to 95% by mass.
- the amount of the non-volatile component is measured based on a mass change after being held at 150 ° C. for 45 minutes.
- the composition for forming a hard coat layer containing an organopolysiloxane as a main component is 50% or more of the organopolysiloxane with respect to the total amount of each component of the composition for forming a hard coat layer excluding the solvent. It shows that it contains.
- the hard coat layer forming composition used in the present invention may contain various additives in addition to the organopolysiloxane.
- a composition for forming a hard coat layer containing silica fine particles is preferable.
- colloidal silica refers to silica fine particles dispersed in water or an organic solvent such as methanol, ethanol, isobutanol, or propylene glycol monomethyl ether.
- the silica fine particles can be blended with the raw material monomer in the process of producing the organopolysiloxane.
- organopolysiloxane in a reaction system containing colloidal silica, an organopolysiloxane containing silica fine particles can be obtained.
- a T monomer and, if necessary, water or an acid catalyst are added to colloidal silica, and the organopolysiloxane can be produced in the colloidal silica dispersion medium as described above.
- a composition for forming a hard coat layer used in the present invention containing silica fine particles can be produced.
- the silica fine particles used in the composition for forming a hard coat layer according to the present invention preferably has an average particle size (BET method) of 1 to 100 nm. If the average particle diameter exceeds 100 nm, the particles diffusely reflect light, and thus the value of the haze value of the obtained hard coat layer becomes large, which may be undesirable in terms of optical quality. Further, the average particle size is particularly preferably 5 to 40 nm. This is for imparting scratch resistance to the hard coat layer and maintaining the transparency of the hard coat layer. Moreover, although colloidal silica can use both a water dispersion type and an organic solvent dispersion type, it is more preferable to use a water dispersion type.
- colloidal silica dispersed in an acidic aqueous solution.
- the colloidal silica may contain inorganic fine particles other than silica fine particles such as alumina sol, titanium sol, and ceria sol.
- the content of the silica fine particles in the hard coat layer forming composition used in the present invention is preferably 1 to 50% by mass, preferably 5 to 40% by mass, based on the total amount of the composition (nonvolatile components) excluding the solvent. Is more preferred.
- the content of the silica fine particles in the nonvolatile component in the composition for forming a hard coat layer used in the present invention is less than 1% by mass, sufficient scratch resistance may not be ensured in the obtained hard coat layer, and the content is If it exceeds 50% by mass, the proportion of organopolysiloxane in the non-volatile component becomes too low, and it becomes difficult to form a cured film by thermosetting organopolysiloxane, and cracks occur in the finally obtained hard coat layer. Or the silica fine particles may aggregate and the transparency of the hard coat layer may be reduced.
- the composition for forming a hard coat layer used in the present invention may further contain additives such as an antifoaming agent and a viscosity modifier for the purpose of improving the coatability, and the purpose of improving the adhesion to the primer layer.
- additives such as an antifoaming agent and a viscosity modifier for the purpose of improving the coatability, and the purpose of improving the adhesion to the primer layer.
- an additive such as an adhesion-imparting agent may be included, and a leveling agent may be included as an additive for the purpose of improving the coatability and the smoothness of the resulting coating film.
- the amount of these additives is preferably 0.01 to 2 parts by mass for each additive component with respect to 100 parts by mass of the organopolysiloxane.
- the composition for forming a hard coat layer used in the present invention may contain a dye, a pigment, a filler and the like as long as the object of the present invention is not impaired.
- the hard coat layer forming composition used in the present invention may further contain a curing catalyst.
- Curing catalysts include aliphatic carboxylic acids (formic acid, acetic acid, propionic acid, butyric acid, lactic acid, tartaric acid, succinic acid, etc.), alkali metal salts such as lithium salt, sodium salt, potassium salt; benzyltrimethylammonium salt, tetramethylammonium salt Quaternary ammonium salts such as salts and tetraethylammonium salts; metal alkoxides and chelates such as aluminum, titanium and cerium; ammonium perchlorate, ammonium chloride, ammonium sulfate, sodium acetate, imidazoles and their salts, ammonium trifluoromethylsulfonate, Bis (tolufluoromethylsulfonyl) bromomethylammonium and the like can be mentioned.
- the blending amount of the curing catalyst is preferably 0.01 to 10 parts by mass, more preferably 0.1 to 5 parts by mass with respect to 100 parts by mass of the organopolysiloxane.
- the content of the curing catalyst is less than 0.01 parts by mass, it is difficult to obtain a sufficient curing rate.
- the content is more than 10 parts by mass, the storage stability of the composition for forming a hard coat layer is reduced, or a precipitate is formed. There are things to do.
- the hard coat layer forming composition used in the present invention preferably further contains an ultraviolet absorber in order to suppress yellowing of the resin substrate.
- an ultraviolet absorber benzophenone UV absorbers, benzotriazole UV absorbers, benzimidazole UV absorbers, cyanoacrylate UV absorbers, salicylate UV absorbers, benzylidene malonate UV absorbers, triazine UV An absorbent etc. are mentioned. These ultraviolet absorbers may be used alone or in combination of two or more. Further, in order to prevent the ultraviolet absorber from bleeding out from the finally obtained hard coat layer, an ultraviolet absorber having a trialkoxysilyl group may be used.
- the ultraviolet absorber having a trialkoxysilyl group is converted into a hydroxyl group by a hydrolysis reaction during the formation of a cured film by thermal curing of the organopolysiloxane, and then incorporated into the cured film by a dehydration condensation reaction. Bleeding out of the absorbent from the hard coat layer can be suppressed.
- Specific examples of such trialkoxysilyl groups include trimethoxysilyl groups and triethoxysilyl groups.
- the content of the ultraviolet absorber in the hard coat layer forming composition is preferably 0.1 to 50 parts by mass, and preferably 0.1 to 30 parts by mass with respect to 100 parts by mass of the organopolysiloxane. Is particularly preferred.
- the pH of the hard coat layer forming composition is adjusted to 2.0 to 7.0. It is preferable to adjust to 3.0 to 6.0, more preferably to 3.0 to 6.0, and further preferably to 4.0 to 5.5. Under conditions where the pH is less than 2.0 or more than 7.0, the hydroxyl group bonded to the silicon atom is extremely unstable and is not suitable for storage. Examples of the pH adjustment method include addition of an acid and adjustment of the content of the curing catalyst.
- Acids include inorganic acids such as hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, nitrous acid, perchloric acid, sulfamic acid; formic acid, acetic acid, propionic acid, butyric acid, oxalic acid, succinic acid, maleic acid, lactic acid, p-toluene
- examples include organic acids such as sulfonic acid.
- the composition for forming a hard coat layer used in the present invention is usually prepared in a form in which organopolysiloxane as an essential component and various additives as optional components are dissolved and dispersed in a solvent. It is necessary that all the non-volatile components in the composition for forming a hard coat layer be stably dissolved and dispersed in a solvent.
- the solvent is contained at least 20% by mass, preferably 50% by mass or more. More preferably, the alcohol solvent is contained at least 20% by mass, preferably 50% by mass or more.
- alcohols used in such solvents include methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, 2-methyl-1-propanol, 1-methoxy-2-propanol, and 2-ethoxyethanol.
- Diacetone alcohol, 2-butoxyethanol and the like are preferable.
- alcohol having a boiling point of 80 to 160 ° C. is preferable from the viewpoint of good solubility of the organopolysiloxane and good coating property.
- ethanol 1-propanol, 2-propanol, 1-butanol, 2-butanol, 2-methyl-1-propanol, 1-methoxy-2-propanol, 2-ethoxyethanol, diacetone alcohol, and 2 -Butoxyethanol is preferred.
- the solvent used in the composition for forming a hard coat layer used in the present invention includes, for example, a lower alcohol generated by hydrolyzing a raw material monomer, for example, an alkyltrialkoxysilane, when an organopolysiloxane is produced.
- a raw material monomer for example, an alkyltrialkoxysilane
- the dispersed organic solvent is also included.
- a solvent other than the above a solvent other than alcohol that can be mixed with water / alcohol may be used in combination.
- Ketones such as acetone and acetylacetone; esters such as ethyl acetate and isobutyl acetate; ethers such as propylene glycol monomethyl ether, dipropylene glycol monomethyl ether and diisopropyl ether.
- the amount of the solvent used in the composition for forming a hard coat layer according to the present invention is preferably 50 to 3000 parts by mass, and preferably 150 to More preferably, it is 2000 parts by mass.
- composition for forming a hard coat layer used in the present invention can be obtained by uniformly mixing the various components described above by ordinary methods.
- the resin substrate with a hard coat film of the present invention is formed by applying the hard coat layer forming composition on the acrylic primer layer obtained above to form a coating film, and the organopolysiloxane in the coating film. It can manufacture by hardening the curable composition which has as a main component and making it a hard-coat layer.
- the method for applying the hard coat layer-forming composition is not particularly limited, and examples thereof include usual coating methods such as spray coating, dip coating, flow coating, die coating, and spin coating. It is preferable to appropriately adjust the viscosity, solid content concentration and the like of the composition for forming a hard coat layer according to the coating method to be used.
- the composition for forming a silicone-based hard coat layer applied on the acrylic primer layer is usually after the solvent is dried and removed under a temperature condition of 0 ° C. or higher and lower than the thermal deformation temperature of the resin substrate / primer layer, Heat cured.
- the solvent drying conditions include 0 to 60 ° C. and 10 minutes to 10 hours.
- the thermosetting reaction is preferably performed at a high temperature within a range where there is no problem in the heat resistance of the resin substrate and the primer layer, so that the curing can be completed more quickly.
- the curing temperature is preferably 50 to 200 ° C., particularly preferably 80 to 160 ° C., and particularly preferably 100 to 140 ° C.
- the curing time is preferably 10 minutes to 4 hours, particularly preferably 20 minutes to 3 hours, particularly preferably 30 minutes to 2 hours.
- the thickness of the coating film formed by applying the composition for forming a hard coat layer on the surface of a resin substrate or the like depends on the solid content concentration in the composition. It is preferable to adjust the solid content appropriately so that the film thickness after curing is within a predetermined range.
- the film thickness of the cured film applied on the resin substrate is preferably 0.1 ⁇ m or more and 10 ⁇ m or less, and more preferably 1 ⁇ m or more and 8 ⁇ m or less in the state after curing described below. It is particularly preferably 2 ⁇ m or more and 7 ⁇ m or less. If the thickness of the hard coat layer is too small, it may be difficult to ensure sufficient scratch resistance. On the other hand, if the thickness of the hard coat layer is too large, cracks and peeling may occur easily. Therefore, in order to suppress the occurrence of cracks and peeling while ensuring sufficient scratch resistance, the film thickness of the cured film (that is, the film thickness of the hard coat layer) is 0.1 ⁇ m or more and 10 ⁇ m or less. It is preferable. In addition, this film thickness means the thickness when a hard coat layer is formed alone on a substrate such as a resin substrate.
- a technique for forming the top coat layer whose main component is SiO 2 it is preferable to apply a technique of applying poly (perhydro) silazane on the hard coat layer and curing, or a technique such as vapor deposition or sputtering.
- the resin substrate 1 with a hard coat film of this invention was demonstrated, it is not necessarily limited to such a structure, Moreover, about the formation order of each part, etc. in the limit which can manufacture the resin substrate 1 with a hard coat film. It can be changed as appropriate.
- Examples 1 to 5 are examples, and examples 6 to 9 are comparative examples.
- Mn, Mw, and Mw / Mn of polymethyl methacrylate are obtained by gel permeation chromatography (GPC, HLC-8220GPC manufactured by Tosoh Corporation, RI detection, column: TSK guard column Super HZ-L + TSK gel Super HZ 4000 + HZ 3000 + HZ 2500 + HZ 2000), eluent: THF It was.
- a primer layer composition was prepared by the method shown below. Mw of the obtained resin and the like was determined by gel permeation chromatography as described above.
- the solution thus obtained was diluted with 1-methoxy-2-propanol to have a nonvolatile content of 10% by mass, and a hydrolyzable silyl group-containing acrylic polymer (referred to as a silyl group-containing acrylic polymer) solution S-1.
- a hydrolyzable silyl group-containing acrylic polymer referred to as a silyl group-containing acrylic polymer
- Mw (weight average molecular weight) of the obtained silyl group-containing acrylic polymer was 114,000.
- the weight average molecular weight of the obtained silyl group-containing acrylic polymer was 68,000.
- the weight average molecular weight of the obtained silyl group-containing acrylic polymer was 66,000.
- a 0.5 liter flask equipped with a stirrer, a condenser and a thermometer was charged with 41 g of diacetone alcohol as a solvent, and heated to 80 ° C. under a nitrogen stream.
- 66 g of the monomer mixed solution and 15 g of the polymerization initiator solution prepared in advance were sequentially added.
- the remaining monomer mixed solution and the remaining polymerization initiator solution were simultaneously added dropwise at 80 to 90 ° C. over 1.5 hours.
- the mixture was further stirred at 80 to 90 ° C. for 5 hours.
- the obtained solution was diluted with 1-methoxy-2-propanol to have a nonvolatile content of 10% by mass to obtain a silyl group-containing acrylic polymer solution S-4.
- Mw of the obtained silyl group-containing acrylic polymer was 71,000.
- Primer composition ⁇ Primer layer forming composition (primer composition)> (Preparation Example 1) 80 g of polymethyl methacrylate solution (P-1) and 20 g of silyl group-containing acrylic polymer solution (S-1) (mass ratio of 80:20 in terms of solid content) were mixed, and dibenzoresorcinol (DBR) was further used as an ultraviolet absorber. And 0.8 g of triazine ultraviolet absorber (TINUVIN477, manufactured by BASF) were added to obtain a primer layer forming composition Pr-1.
- DBR dibenzoresorcinol
- TINUVIN477 triazine ultraviolet absorber
- Preparation Example 2 60 g of polymethyl methacrylate solution (P-1) and 40 g of silyl group-containing acrylic polymer solution (S-1) (mass ratio of 60:40 in terms of solid content) were mixed, and dibenzoresorcinol (DBR) was further used as an ultraviolet absorber. 0.6 g of Clariant) and 0.4 g of triazine ultraviolet absorber (TINUVIN477, manufactured by BASF) were added to obtain a primer layer forming composition Pr-2.
- DBR dibenzoresorcinol
- Preparation Example 3 80 g of polymethyl methacrylate solution (P-1) and 20 g of silyl group-containing acrylic polymer solution (S-2) (mass ratio of 80:20 in terms of solid content) were mixed, and dibenzoresorcinol (DBR) was further used as an ultraviolet absorber. And 0.8 g of triazine ultraviolet absorber (TINUVIN477, manufactured by BASF) were added to obtain a primer layer forming composition Pr-3.
- DBR dibenzoresorcinol
- Preparation Example 4 60 g of polymethyl methacrylate solution (P-1) and 40 g of a silyl group-containing acrylic polymer solution (S-2) (mass ratio of 60:40 in terms of solid content) are mixed, and dibenzoresorcinol (DBR) is further used as an ultraviolet absorber. 0.6 g of Clariant) and 0.4 g of triazine ultraviolet absorber (TINUVIN477, manufactured by BASF) were added to obtain a primer layer forming composition Pr-4.
- DBR dibenzoresorcinol
- Preparation Example 5 80 g of polymethyl methacrylate solution (P-1) and 20 g of silyl group-containing acrylic polymer solution (S-3) (mass ratio of 80:20 in terms of solid content) were mixed, and dibenzoresorcinol (DBR) was further used as an ultraviolet absorber. And 0.8 g of triazine-based ultraviolet absorber (TINUVIN477, manufactured by BASF) were added to obtain a primer layer forming composition Pr-5.
- DBR dibenzoresorcinol
- Preparation Example 6 100 g of polymethyl methacrylate solution (P-1) was charged with 0.8 g of dibenzoresorcinol (DBR, Clariant) and 0.2 g of triazine UV absorber (TINUVIN477, BASF) as UV absorbers. A primer layer forming composition Pr-6 was obtained.
- DBR dibenzoresorcinol
- TINUVIN477 triazine UV absorber
- Preparation Example 7 80 g of polymethyl methacrylate solution (P-1) and 20 g of silyl group-containing acrylic polymer solution (S-4) were mixed, and 0.8 g of dibenzoresorcinol (DBR, Clariant) was added as an ultraviolet absorber. As a result, a primer layer forming composition Pr-7 was obtained.
- DBR dibenzoresorcinol
- Preparation Example 8 40 g of a polymethyl methacrylate solution (P-1) and 60 g of a silyl group-containing acrylic polymer solution (S-1) are mixed, and 0.4 g of dibenzoresorcinol (DBR, manufactured by Clariant) as a UV absorber and triazine UV An absorbent (TINUVIN477, manufactured by BASF) (0.6 g) was added to obtain a primer layer forming composition Pr-8.
- DBR dibenzoresorcinol
- TINUVIN477 manufactured by BASF
- hard coat agent composition ⁇ Hardcoat layer forming composition (hardcoat agent composition)>
- the hard coat agent composition was prepared by the method shown below.
- the organopolysiloxane was evaluated by the following method.
- the bonding state of silicon atom in organopolysiloxane is determined by a nuclear magnetic resonance apparatus ( 29 Si -NMR: Each was determined from the peak area ratio of 29 Si-NMR using ECP400) manufactured by JEOL Ltd.
- the measurement conditions were a polytetrafluoroethylene (PTFE) 10 mm ⁇ sample tube, proton decoupling, pulse width 45 °, waiting time 15 sec, relaxation reagent: Cr (acac) 3 (tris (acetylacetonato) chromium) of 0. 1% by mass, external standard sample: tetramethylsilane.
- PTFE polytetrafluoroethylene
- the chemical shift of 29 Si-NMR derived from each structure is as follows. T0: ⁇ 40 to ⁇ 41 ppm, T1: -49 to -50 ppm, T2: -57 to -59 ppm, T3: -66 to -70 ppm.
- methyl silicone resin KR-500 manufactured by Shin-Etsu Chemical Co., Ltd., the peak derived from the Si—OH group was not confirmed by FT-IR, but only SiO—CH 3 .
- MSi-1 was compared with the raw material KR-500 by FT-IR and 1 H-NMR. As a result, a decrease in the peak derived from the SiO—CH 3 group and a peak derived from the Si—OH group were observed. Confirmed the appearance of.
- the Mn of MSi-1 was 520, Mw was 1150, and Mw / Mn was 2.22.
- the resulting organopolysiloxane (b) is substantially free of monomeric T0 form [R—Si (OH) 3 ] (R is CH 3 ), and the raw material methyltrimethoxysilane is an oligomeric silicone compound. It was confirmed that it was almost completely converted.
- Mn of the obtained component (b) organopolysiloxane PSi-1 was 400, Mw was 670, and Mw / Mn was 1.68.
- composition for forming hard coat layer (b) Component organopolysiloxane obtained in [2] above was added to the solution containing component (a) organopolysiloxane MSi-1 obtained in [1] above.
- Examples 1 to 5 and Example 6 to 9 was prepared as a resin substrate with a hard coat film.
- the film thickness of the following primer layers and hard coat layers was the thickness of each layer formed on the polycarbonate plate alone, and was measured using an interference film thickness measuring apparatus (Spectra Corp Corp., Solid Lambda Thickness).
- Example 1 A primer layer-forming composition Pr-1 was applied to a polycarbonate resin plate (Carbo Glass (registered trademark) Polish Clear (trade name, manufactured by Asahi Glass Co., Ltd.)) with a thickness of 3 mm so as to have a film thickness of 4 ⁇ m by dip coating. Then, after being left at 25 ° C. for 20 minutes, it was cured by heating at 120 ° C. for 30 minutes using a hot air circulating dryer (manufactured by Enomoto Kasei Co., Ltd., HISPEC HS250).
- a polycarbonate resin plate Carbo Glass (registered trademark) Polish Clear (trade name, manufactured by Asahi Glass Co., Ltd.)
- a hot air circulating dryer manufactured by Enomoto Kasei Co., Ltd., HISPEC HS250.
- the hard coat layer forming composition HC-1 was applied by a dip coating method so as to have a film thickness of 3 ⁇ m, left at 25 ° C. for 20 minutes, and then at 120 ° C. It was cured by heating for 1 hour to prepare a resin substrate with a hard coat film.
- Example 2 A resin substrate with a hard coat film was prepared in the same manner as in Example 1 except that the primer layer forming composition Pr-2 was applied to a film thickness of 5 ⁇ m instead of the primer layer forming composition Pr-1. Produced.
- Example 3 A resin substrate with a hard coat film was prepared in the same manner as in Example 1 except that the primer layer forming composition Pr-3 was applied instead of the primer layer forming composition Pr-1.
- Example 4 A resin substrate with a hard coat film was prepared in the same manner as in Example 1 except that the primer layer forming composition Pr-4 was applied instead of the primer layer forming composition Pr-1.
- Example 5 A resin substrate with a hard coat film was prepared in the same manner as in Example 1 except that the primer layer forming composition Pr-5 was applied to a film thickness of 5 ⁇ m instead of the primer layer forming composition Pr-1. Produced.
- Example 6 A resin substrate with a hard coat film was produced in the same manner as in Example 1 except that the primer layer forming composition Pr-6 was applied instead of the primer layer forming composition Pr-1.
- Example 7 A resin substrate with a hard coat film was prepared in the same manner as in Example 1 except that the primer layer forming composition Pr-7 was applied so as to have a film thickness of 5 ⁇ m instead of the primer layer forming composition Pr-1. Produced.
- Example 8 Resin substrate with a hard coat film in the same manner as in Example 1 except that the primer layer forming composition Pr-8 was applied to a film thickness of 5 ⁇ m instead of the primer layer forming composition Pr-1 was made.
- Example 9 A resin substrate with a hard coat film was prepared in the same manner as in Example 1 except that the primer layer forming composition Pr-9 was applied so as to have a film thickness of 5 ⁇ m instead of the primer layer forming composition Pr-1. Produced.
- the haze (haze value) after 500 rotations under a load of 500 g was measured, and the haze (haze value) difference ⁇ H 500 before and after the test was defined as scratch resistance.
- scratch resistance As a criterion for determination of scratch resistance, if ⁇ H 500 ⁇ + 10, it is determined to be acceptable.
- ⁇ 2> Weather resistance test The following weather resistance test was performed. That is, an accelerated weathering tester using a metal halide lamp as a light source (Daipura Wintes; Daipla Metal Weather “KW-R5TP-A”) is used for 50 cycles (3 conditions of light irradiation, condensation, and darkness) 600 hours).
- the light irradiation conditions were as follows: illuminance of 80 mW / cm 2 (produced by USHIO INC., Trade name “UIT-101”), black panel temperature of 63 ° C. and relative humidity of 80%.
- Irradiation is performed, and the conditions for condensation are those in which the black panel temperature is naturally cooled from 63 ° C. to 30 ° C. and maintained for 4 hours at 98% relative humidity without irradiation with light. Is kept for 4 hours at a black panel temperature of 75 ° C. and a relative humidity of 90%.
- a shower is performed for 10 seconds before and after the dew condensation.
- the initial haze (cloudiness value) is small.
- the appearance was good, the haze (cloudiness value) difference after the Taber test was 10 or less, and the scratch resistance was acceptable.
- the appearance of the hard coat film after the weather resistance test was good and the weather adhesion was also excellent, and the adhesion between the hard coat layer and the primer layer was improved.
- the haze (Haze value) is small and the appearance is good, and the scratch resistance is also acceptable, but after the weather resistance test, cracks and peeling occur in the hard coat film, the appearance judgment after the weather resistance test is "x", and the adhesion The nature was bad.
- the value of (content of acrylic polymer (P)) / (total content of acrylic polymer (P) and content of silyl group-containing acrylic polymer ( ⁇ )) in the primer layer is 50 mass.
- % of the resin substrate with a hard coat film of Example 8 and the resin substrate with a hard coat film of Example 9 in which the primer layer does not have an acrylic polymer (P) the haze (cloudiness value) is large in the initial stage. The coat film was cracked and peeled, and the appearance was inferior, the appearance after the weather resistance test was “x”, and the adhesion was poor.
- the resin substrate with a hard coat film of the present invention can be suitably used as a window glass for vehicles attached to automobiles and various transportation facilities, and a window glass for building materials attached to buildings such as houses and buildings.
- a window glass for vehicles attached to automobiles and various transportation facilities and a window glass for building materials attached to buildings such as houses and buildings.
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Abstract
Description
透明樹脂板の耐擦傷性および耐候性を向上させる目的で、種々のハードコート剤、特にシリコーン系ハードコート剤を用いて透明樹脂板の表面に被膜を形成することが提案されている。また、その際、ハードコート層と透明樹脂板との密着性を向上させるために、プライマー層等の接着層を介在させることも検討されている。
また、前記シリル基含有アクリル系ポリマー(α)は、前記メタクリル酸メチル(MMA)に基づく重合単位、ならびに前記加水分解性シリル基および/またはSiOH基を有する重合単位から成り、前記メタクリル酸メチル(MMA)に基づく重合単位と、前記加水分解性シリル基および/またはSiOH基を有する重合単位とのモル比が、50:50~95:5であることが好ましい。
また、前記加水分解性シリル基および/またはSiOH基を有する重合単位は、3-メタクリロキシプロピルトリメトキシシラン、3-メタクリロキシプロピルメチルジメトキシシラン、3-メタクリロキシプロピルジメチルメトキシシラン、3-メタクリロキシプロピルトリエトキシシラン、3-メタクリロキシプロピルメチルジエトキシシラン、3-アクリロキシプロピルトリメトキシシランおよび3-アクリロキシプロピルメチルジメトキシシラン、ならびにこれらの加水分解物または部分加水分解物に基づく重合単位からなる群から選ばれる少なくとも1種であることが好ましい。
また、前記シリル基含有アクリル系ポリマー(α)は、ヒドロキシアルキル基を有する重合単位を含有しないことが好ましい。
本明細書において、「ハードコート被膜」とは、樹脂基板上に形成されたハードコート層を含む多層からなる被膜をいう。すなわち、本発明においては、プライマー層、およびハードコート層を有する被膜全体を、「ハードコート被膜」という。
「加水分解性シリル基」とは、ケイ素原子に直接結合された加水分解性基を有するシリル基をいう。ここで、「加水分解性基」とは、加水分解により水酸基(-OH基)となる基をいう。したがって、「加水分解性シリル基および/またはSiOH基」とは、一部が加水分解により水酸基(-OH基)となったものを含めて、ケイ素原子に加水分解性基が結合したシリル基を意味する。なお、「加水分解性シリル基および/またはSiOH基」とは、「加水分解性シリル基およびSiOH基の群から選ばれる少なくとも1種の基を有する」と記載することもできる。加水分解性基の具体例については後で詳述する。
また、本発明のハードコート被膜付き樹脂基板においては、前記プライマー層中にメタクリル酸メチル(MMA)に基づく重合単位、ならびに加水分解性シリル基および/またはSiOH基を有する重合単位を含有するシリル基含有アクリル系ポリマー(α)を含有させたプライマー層3が設けられているので、ハードコート被膜の耐擦傷性が良好であるとともに、ハードコート層4に係る耐候密着性、耐候クラック性等の耐候性にも優れている。
本発明に用いる樹脂基板の材料である樹脂としては、ポリカーボネート樹脂、ポリスチレン樹脂、芳香族ポリエステル樹脂、アクリル樹脂、ポリエステル樹脂、ポリアリレート樹脂、ハロゲン化ビスフェノールAとエチレングリコールとの重縮合物、アクリルウレタン樹脂、ハロゲン化アリール基含有アクリル系ポリマー等の熱可塑性樹脂が挙げられる。
これらのなかでも、芳香族系ポリカーボネート樹脂等のポリカーボネート樹脂やポリメチルメタクリレート系アクリル樹脂等のアクリル樹脂が好ましく、ポリカーボネート樹脂がより好ましい。さらに、ポリカーボネート樹脂のなかでも、特にビスフェノールA系ポリカーボネート樹脂が好ましい。なお、樹脂基板は、上記のような熱可塑性樹脂を2種以上含んでもよいし、これらの樹脂を用いて、2層以上積層された積層基板であってもよい。また、樹脂基板の形状は、特に限定されず、平板であってもよいし、湾曲していてもよい。樹脂基板の色調は、無色透明または着色透明であることが好ましい。
本発明のハードコート被膜付き樹脂基板は、樹脂基板2の少なくとも一方の面上にアクリル系ポリマー(P)およびシリル基含有アクリル系ポリマー(α)を主成分とするプライマー層3を有する。プライマー層3は、樹脂基板2と後述するハードコート層4との密着性を向上させるために設けられる層であり、樹脂基板2と直接接することで樹脂基板2との間の密着性が確保される。
本発明のハードコート被膜付き樹脂基板のプライマー層3においては、主成分として、アクリル系ポリマー(P)、及び下記に述べるシリル基含有アクリル系ポリマー(α)を含有する。
プライマー層3には、上述したアクリル系ポリマー(P)とともに、シリル基含有アクリル系ポリマー(α)が含有されている。
すなわち、本発明のプライマー層は、アクリル系ポリマー(P)およびシリル基含有アクリル系ポリマー(α)を主成分として含有する。ここにおいて、アクリル系ポリマー(P)およびシリル基含有アクリル系ポリマー(α)を主成分とするプライマー層とは、プライマー層におけるアクリル系ポリマー(P)およびシリル基含有アクリル系ポリマー(α)の合計の含有割合が、50質量%以上であることをいう。
各シリル基含有重合単位(α1)に含有される加水分解性シリル基の数は、通常1個であるが2個以上とすることもできる。シリル基含有重合単位(α1)は、主鎖となるアクリル系ポリマーに結合された炭化水素基に、加水分解性シリル基が、C-Si結合を介して結合しているものが好ましい。
また、このシリル基含有アクリル系ポリマー(α)は、芳香族炭化水素基を側鎖に有する重合単位を含有しない。すなわち、紫外線吸収性基のような芳香族炭化水素基を有するモノマーが共重合された構造を有していない。
一方、(アクリル系ポリマー(P)の含有量)/(アクリル系ポリマー(P)の含有量とシリル基含有アクリル系ポリマー(α)の含有量との合計量)×100の値が98質量%を超えると、プライマー層3とハードコート層4との間でシロキサン結合(-O-Si-O-)が十分に形成されず、ハードコート層3との密着性を十分に向上させることが困難となるおそれがある。
このようなシリル基含有アクリル系ポリマー(α)は、(A)C-Si結合を介して結合された加水分解性シリル基を有するアクリル系モノマー(以下、シリル基含有アクリル系モノマーということがある。)と、(B)メタクリル酸メチルとからなるモノマー成分を共重合して得ることができる。
(A)のシリル基含有アクリル系モノマーとしては、1分子中に1個または2個以上のC-Si結合を介して結合された加水分解性シリル基を有し、かつ1個のアクリル基またはメタクリル基を有するモノマーであれば、特に限定されることなく使用することができる。特に、1個の加水分解性シリル基を有するメタクリル酸エステルが好ましい。
メタクリル酸メチル(MMA)に基づく重合単位が50モル%未満であると、シリル基含有アクリル系ポリマー(α)と、プライマー層の主成分であるアクリル系ポリマー(P)との相溶性が低くなるおそれがある。一方、メタクリル酸メチル(MMA)に基づく重合単位が95モル%を超えると、加水分解性シリル基および/またはSiOH基を有する重合単位(α1)の割合が低くなり、ハードコート層のオルガノポリシロキサンに含まれる加水分解性シリル基等との結合部位が不足するため、耐候密着性向上の効果を十分に得られないおそれがある。
加水分解性シリル基および/またはSiOH基を有する重合単位(α1)が5モル%未満では、この重合単位が有する加水分解性シリル基と、後述するハードコート層を構成するオルガノポリシロキサンの有する末端基(例えば、Si-OX基。ただし、-OXは水酸基またはアルコキシ基を示す。)との反応が十分に起こらず、ハードコート層との密着性向上の効果が十分に得られない。また、(A)加水分解性シリル基および/またはSiOH基を有する重合単位(α1)が50モル%を超えると、未反応の加水分解性基が残存し易くなるため、経時での後架橋が形成し、クラックが発生し易くなる場合がある。また、必然的に、メタクリル酸メチル(MMA)に基づく重合単位(α2)が50モル%以下になるため、プライマー層におけるなじみ(相溶性)が悪くなる可能性がある。
特に好ましい共重合組成は、(A)加水分解性シリル基および/またはSiOH基を有する重合単位(α1)が5~40モル%、(B)メタクリル酸メチル(MMA)に基づく重合単位(α2)が60~95モル%である。
シリル基含有アクリル系ポリマー(α)における、(MMAに基づく重合単位(α2)):(シリル基含有重合単位(α1))のモル比、すなわち(MMAに基づく重合単位(α2))/(シリル基含有重合単位(α1))の値が50/50未満であると、プライマー層中での、シリル基含有アクリル系ポリマー(α)と、アクリル系ポリマー(P)との相溶性が低くなるおそれがある。また、未反応の加水分解性基が残存し易くなるため、経時での後架橋が形成し、クラックが発生し易くなる場合もある。一方、(MMAに基づく重合単位(α2))/(シリル基含有重合単位(α1))の値が95/5を超えると、この重合単位が有する加水分解性シリル基と、後述するハードコート層を構成するオルガノポリシロキサンの有する末端基(例えば、Si-OX基。ただし、-OXは水酸基またはアルコキシ基を示す。)との反応が十分に生起せず、ハードコート層との密着性向上の効果が十分に得られないことがある。
メタクリル酸メチル(MMA)に基づく重合単位(α2)と、加水分解性シリル基および/またはSiOH基を有する重合単位(α1)とのモル比は、より好ましくは60:40~90:10であることが好ましい。
一方、シリル基含有アクリル系ポリマー(α)の質量平均分子量が5,000未満であると、プライマー層中でのアクリル系ポリマーとの絡み合いが弱くなり、プライマー層3の強度が低下するおそれがある。
(オルガノポリシロキサン)
本発明のハードコート被膜付き樹脂基板に用いるハードコート層は、主成分としてオルガノポリシロキサンの硬化物を含有するが、この硬化物を形成するポリオルガノシロキサンとしては、硬化性のポリオルガノシロキサンであれば、特に制限なく用いることができる。
なお、オルガノポリシロキサンにおけるM単位、D単位、T単位、Q単位の数の割合は、29Si-NMRによるピーク面積比の値から計算できる。
T2:R-Si(-OX)(-O*-)2
T3:R-Si(-O*-)3
(式中、Rは、水素原子または炭素数が1~10の置換または非置換の1価の有機基を表し、Xは、水素原子または炭素数1~6のアルキル基を表し、O*は2つのケイ素原子を連結する酸素原子を表す。)
3-クロロプロピル基、3,3,3-トリフルオロプロピル基、3-メルカプトプロピル基、p-メルカプトメチルフェニルエチル基、3-アクリロイルオキシプロピル基、3-メタクリロイルオキシプロピル基、3-グリシドキシプロピル基、2-(3,4-エポキシシクロヘキシル)エチル基、3-アミノプロピル基、N-フェニル-3-アミノプロピル基、N-(2-アミノエチル)-3-アミノプロピル基、2-シアノエチル基。
なお、本発明のハードコート被膜付き樹脂基板においては、ハードコート層を形成するために、通常用いられる、ハードコート層を構成する成分の硬化前の材料を含有する組成物(以下、「ハードコート層形成用組成物」という。)を調製しこれを用いる。本発明に好ましく用いられる硬化性のオルガノポリシロキサン(T)についても、製造過程において、このようなハードコート層形成用組成物に配合することで、得られるハードコート層にその硬化物として含有させることが可能となる。
オルガノポリシロキサン(a)は、T1~T3の各単位を、T1:T2:T3=0~5:15~40:55~85、かつT3/T2=1.5~4.0の割合で含む。また、オルガノポリシロキサン(a)中のOX基について、それがアルコキシ基である個数(A)とそれが水酸基である個数(B)との割合、すなわち(B)/(A)が、分子平均で12.0以上である。かつ、オルガノポリシロキサン(a)の質量平均分子量は800~8000である。なお、オルガノポリシロキサン(a)は、TモノマーであるT0を実質的に含まない。
本発明に用いるハードコート層形成用組成物に上記オルガノポリシロキサン(a)と組合わせて用いるオルガノポリシロキサン(b)は、オルガノポリシロキサン(a)の質量平均分子量の1/10~1/1.5倍の質量平均分子量を有するオルガノポリシロキサンである。オルガノポリシロキサン(b)は、組み合わされるオルガノポリシロキサン(a)よりも質量平均分子量の小さいオルガノポリシロキサンであり、前記T1~T3単位を有する。T1、T2、T3の数の比、T3/T2の割合、(B)/(A)の比は特に限定されない。
本発明において、オルガノポリシロキサンを主成分として含有するハードコート層形成用組成物とは、溶媒を除いたハードコート層形成用組成物の各成分の合量に対し、オルガノポリシロキサンを50%以上含有することを示す。
本発明に用いるハードコート層形成用組成物には、上記オルガノポリシロキサンの他に、種々の添加剤が含まれていてもよい。たとえば、本発明のハードコート層を有する樹脂基板のハードコート層の耐擦傷性をさらに向上させるためには、シリカ微粒子が含まれるハードコート層形成用組成物が好ましい。このために、ハードコート層形成用組成物にコロイダルシリカを配合することが好ましい。なお、コロイダルシリカとは、シリカ微粒子が、水またはメタノール、エタノール、イソブタノール、プロピレングリコールモノメチルエーテル等の有機溶媒中に分散されたものをいう。
本発明のハードコート被膜付き樹脂基板は、上記のハードコート層形成用組成物を、上記で得られたアクリル系プライマー層上に塗布して塗膜を形成し、前記塗膜中のオルガノポリシロキサンを主成分とする硬化性組成物を硬化させてハードコート層とすることにより製造することができる。
上記ハードコート層形成用組成物を塗布する方法としては、特に限定されないが、スプレーコート法、ディップコート法、フローコート法、ダイコート法、スピンコート法等の通常の塗工方法が挙げられる。用いる塗工方法に応じて、ハードコート層形成用組成物の粘度、固形分濃度等を適宜調整することが好ましい。
ハードコート層の膜厚が小さすぎると、十分な耐擦傷性を確保することが困難である可能性がある。一方、ハードコート層の膜厚が大きすぎると、クラックや剥離が発生しやすくなるおそれがある。よって、十分な耐擦傷性を確保しつつ、クラックや剥離の発生を抑制するためには、硬化膜の膜厚(すなわち、ハードコート層の膜厚)は、0.1μm以上、10μm以下であることが好ましい。
なお、この膜厚は、樹脂基板のような基板上にハードコート層を単独で成膜したときの厚さを意味する。
ポリメタクリル酸メチル(PMMA)(数平均分子量Mn=120,000、質量平均分子量Mw=340,000、分散度Mw/Mn=2.8)を、1メトキシ2プロパノール:ジアセトンアルコール=85:15(質量比)からなる溶媒に溶解し、不揮発分が10質量%となるように調整し、プライマー組成物であるポリメタクリル酸メチル溶液P-1を得た。
(合成例1)
撹拌機、コンデンサー及び温度計を備えた0.5リットルフラスコに、窒素気流下で、メチルメタクリレート(MMA)90gと3-メタクリルオキシプロピルトリメトキシシラン(MPTM)を25g、およびジアセトンアルコール200gを混合したものを入れ80℃に加熱した。その後、重合開始剤として2、2’-アゾビス(2-メチルブチロニトリル)0.7gを投入し、80~90℃で3時間撹拌し、MMAとMPTAとを共重合させた。なお、モノマー成分であるMMAとMPTMとのモル比は、90:10であった。
こうして得られた溶液を、1-メトキシ-2-プロパノールで希釈して不揮発分を10質量%とし、加水分解性シリル基含有アクリル系ポリマー(シリル基含有アクリル系ポリマーと示す。)溶液S-1を得た。
撹拌機、コンデンサー及び温度計を備えた0.5リットルフラスコに、窒素気流下で、メチルメタクリレート(MMA)80gとγ-メタクリルオキシプロピルトリメトキシシラン(MPTA)を50g、およびジアセトンアルコール200gを混合したものを入れ、80℃に加熱した。その後、重合開始剤として2、2’-アゾビス(2-メチルブチロニトリル)0.7gを投入し、80~90℃で3時間撹拌し、MMAとMPTAとを共重合させた。なお、モノマー成分であるMMAとMPTAとのモル比は、80:20であった。
こうして得られた溶液を、1-メトキシ-2-プロパノールで希釈して不揮発分を10質量%とし、シリル基含有アクリル系ポリマー溶液S-2を得た。
撹拌機、コンデンサー及び温度計を備えた0.5リットルフラスコに、窒素気流下で、メチルメタクリレート(MMA)60gとγ-メタクリルオキシプロピルトリメトキシシラン(MPTA)100g、およびジアセトンアルコール200gを混合したものを入れ80℃に加熱した。その後、重合開始剤として2、2’-アゾビス(2-メチルブチロニトリル)0.8gを投入し、80~90℃で3時間撹拌し、MMAとMPTAとを共重合させた。なお、モノマー成分であるMMAとMPTAとのモル比は、60:40であった。こうして得られた溶液を1-メトキシ-2-プロパノールで希釈して不揮発分を10質量%とし、シリル基含有アクリル系ポリマー溶液S-3を得た。
2-[2’-ヒドロキシ-5’-(2-メタクリロキシエチル)フェニル]-2H-ベンゾトリアゾール(RUVA-93、大塚化学(株)製)22g、γ-メタクリルオキシプロピルトリメトキシシラン(MPTA)を25g、メチルメタクリレート(MMA)70g、グリシジルメタクリレート(GMA)6g、4-メチル-2-ペンタノン96gを混合したものを、単量体混合溶液とした。
(調製例1)
ポリメタクリル酸メチル溶液(P-1)80g、シリル基含有アクリル系ポリマー溶液(S-1)20g(固形分濃度で80:20の質量比)を混合し、さらに紫外線吸収剤としてジベンゾレゾルシノール(DBR、クラリアント社製)0.8gとトリアジン系紫外線吸収剤(TINUVIN477、BASF社製)0.2gを投入して、プライマー層形成用組成物Pr-1を得た。
ポリメタクリル酸メチル溶液(P-1)60g、シリル基含有アクリル系ポリマー溶液(S-1)40g(固形分濃度で60:40の質量比)を混合し、さらに紫外線吸収剤としてジベンゾレゾルシノール(DBR、クラリアント社製)0.6gとトリアジン系紫外線吸収剤(TINUVIN477、BASF社製)0.4gを投入して、プライマー層形成用組成物Pr-2を得た。
ポリメタクリル酸メチル溶液(P-1)80g、シリル基含有アクリル系ポリマー溶液(S-2)20g(固形分濃度で80:20の質量比)を混合し、さらに紫外線吸収剤としてジベンゾレゾルシノール(DBR、クラリアント社製)0.8gとトリアジン系紫外線吸収剤(TINUVIN477、BASF社製)0.2gを投入して、プライマー層形成用組成物Pr-3を得た。
ポリメタクリル酸メチル溶液(P-1)60g、シリル基含有アクリル系ポリマー溶液(S-2)40g(固形分濃度で60:40の質量比)を混合し、さらに紫外線吸収剤としてジベンゾレゾルシノール(DBR、クラリアント社製)0.6gとトリアジン系紫外線吸収剤(TINUVIN477、BASF社製)0.4gを投入して、プライマー層形成用組成物Pr-4を得た。
ポリメタクリル酸メチル溶液(P-1)80g、シリル基含有アクリル系ポリマー溶液(S-3)20g(固形分濃度で80:20の質量比)を混合し、さらに紫外線吸収剤としてジベンゾレゾルシノール(DBR、クラリアント社製)0.8gとトリアジン系紫外線吸収剤(TINUVIN477、BASF社製)0.2gを投入して、プライマー層形成用組成物Pr-5を得た。
ポリメタクリル酸メチル溶液(P-1)100gに、紫外線吸収剤としてジベンゾレゾルシノール(DBR、クラリアント社製)0.8gとトリアジン系紫外線吸収剤(TINUVIN477、BASF社製)0.2gを投入して、プライマー層形成用組成物Pr-6を得た。
ポリメタクリル酸メチル溶液(P-1)80g、シリル基含有アクリル系ポリマー溶液(S-4)20gを混合し、さらに紫外線吸収剤としてジベンゾレゾルシノール(DBR、クラリアント社製)0.8gを投入して、プライマー層形成用組成物Pr-7を得た。
ポリメタクリル酸メチル溶液(P-1)40g、シリル基含有アクリル系ポリマー溶液(S-1)60gを混合し、さらに紫外線吸収剤としてジベンゾレゾルシノール(DBR、クラリアント社製)0.4gとトリアジン系紫外線吸収剤(TINUVIN477、BASF社製)0.6gを投入して、プライマー層形成用組成物Pr-8を得た。
シリル基含有アクリル系ポリマー溶液(S-1)100gへ、紫外線吸収剤としてジベンゾレゾルシノール(DBR、クラリアント社製)0.4gとトリアジン系紫外線吸収剤(TINUVIN477、BASF社製)0.6gを投入して、プライマー層形成用組成物Pr-9を得た。
以下に示す方法で、ハードコート剤組成物を調整した。なお、オルガノポリシロキサンの評価を以下に示す方法によって行った。
実施例において用いたオルガノポリシロキサンは、ケイ素原子結合アルコキシ基として、ケイ素原子結合メトキシ基(SiO-CH3)を有するもののみであったため、上記(B)/(A)として、以下の方法により求めたSi-OH/SiO-CH3の比を用いた。
すなわち、赤外吸光分析装置(FT-IR、サーモフィッシャーサイエンティフィック社製、型式:Avatar/Nicolet FT-IR360)を使用し、900cm-1付近のSi-OHに由来する吸収と、2860cm-1付近のSiO-CH3に由来する吸収との面積比から、Si-OH/SiO-CH3の面積比を求めた。
オルガノポリシロキサン中のケイ素原子の結合状態、具体的には、T0~T3の存在比を、核磁気共鳴装置(29Si-NMR:日本電子株式会社製、ECP400)を用いて、29Si-NMRのピーク面積比からそれぞれ求めた。測定条件は、ポリテトラフルオロエチレン(PTFE)製10mmφ試料管使用、プロトンデカップリング、パルス幅45°、待ち時間15sec、緩和試薬:Cr(acac)3(トリス(アセチルアセトナト)クロム)を0.1質量%、外部標準試料:テトラメチルシランである。また、各構造に由来する29Si-NMRの化学シフトは、以下のとおりである。
T0:-40~-41ppm、
T1:-49~-50ppm、
T2:-57~-59ppm、
T3:-66~-70ppm。
ゲルパーミエーションクロマトグラフィー(GPC、Waters社製のWaters2695、RI検出、カラム:Styragel ガードカラム+HR1+HR4+HR5E、溶離液:クロロホルム)によって求めた。
上記[1]で得られた(a)成分オルガノポリシロキサンMSi-1を含む溶液に、上記[2]で得られた(b)成分オルガノポリシロキサンPSi-1を含む組成物溶液を、MSi-1:PSi-1=80:20(質量比)で配合し、よく混合することによって、ハードコート層形成用組成物HC-1を得た。
上記で得られたプライマー層形成用組成物、およびハードコート層形成用組成物を用い、以下に示すようにして、例1~5および例6~9のハードコート被膜付き樹脂基板を作製した。なお、以下のプライマー層およびハードコート層の膜厚は、ポリカーボネート板上に単独で形成された各層の厚さとし、干渉膜厚測定装置(スペクトラ・コープ社製、Solid Lambda Thickness)を用いて測定した。このとき、屈折率はプライマー層n=1.56、ハードコート層n=1.46の値を用いた。すなわち、ポリカーボネート板上に単独で成膜したときに、膜厚がその値になるように成膜条件を設定し、その条件で各層を形成した。
厚さ3mmのポリカーボネート樹脂板(カーボグラス(登録商標) ポリッシュ クリヤー(商品名、旭硝子社製))に、プライマー層形成用組成物Pr-1をディップコート方式で膜厚が4μmとなるように塗布し、25℃で20分間放置後、熱風循環式乾燥器(楠本化成社製、HISPEC HS250)を使用し、120℃で30分間加熱して硬化させた。
プライマー層形成用組成物Pr-1に代えて、プライマー層形成用組成物Pr-2を膜厚が5μmとなるように塗布したこと以外は、例1と同様にしてハードコート被膜付き樹脂基板を作製した。
プライマー層形成用組成物Pr-1に代えて、プライマー層形成用組成物Pr-3を塗布したこと以外は、例1と同様にしてハードコート被膜付き樹脂基板を作製した。
プライマー層形成用組成物Pr-1に代えて、プライマー層形成用組成物Pr-4を塗布したこと以外は、例1と同様にしてハードコート被膜付き樹脂基板を作製した。
プライマー層形成用組成物Pr-1に代えて、プライマー層形成用組成物Pr-5を膜厚が5μmとなるように塗布したこと以外は、例1と同様にしてハードコート被膜付き樹脂基板を作製した。
プライマー層形成用組成物Pr-1に代えて、プライマー層形成用組成物Pr-6を塗布したこと以外は、例1と同様にしてハードコート被膜付き樹脂基板を作製した。
プライマー層形成用組成物Pr-1に代えて、プライマー層形成用組成物Pr-7を膜厚が5μmとなるように塗布したこと以外は、例1と同様にしてハードコート被膜付き樹脂基板を作製した。
プライマー層形成用組成物Pr-1に代えて、プライマー層形成用組成物Pr-8を膜厚が5μmとなるように塗布したこと以外は、例1と同様にして、ハードコート被膜付き樹脂基板を作製した。
プライマー層形成用組成物Pr-1に代えて、プライマー層形成用組成物Pr-9を膜厚が5μmとなるように塗布したこと以外は、例1と同様にしてハードコート被膜付き樹脂基板を作製した。
上記例1~5および例6~9でそれぞれ得られたハードコート被膜付き樹脂基板について、下記項目の評価を行った。表1に、初期における外観、密着性、曇価(ヘーズ)、耐擦傷性、および耐候性試験後の外観(耐候クラック性)、耐候密着性の測定・評価の結果を、プライマー組成物の種類およびハードコート被膜を構成する各層の膜厚とともに示す。
<1-1>初期外観
初期のハードコート被膜の外観を目視によって観察し、下記基準にしたがって異常の有無を判定した。
○:異常なし。
×:ハードコート被膜にクラック、剥離または著しいヘーズ有り。
各ハードコート層の膜厚を干渉膜厚測定装置(スペクトラ・コープ社製、Solid Lambda Thickness)を用いて測定した。このとき、屈折率は、プライマー層ではn=1.56、ハードコート層ではn=1.46の値を用いた。
JIS K7105(6.4)に準拠し、ヘーズメーター(スガ試験機株式会社製、型式:HGM-2)により、ヘーズ(曇価)を測定した。ヘーズ5以下であれば合格と判定される。
JIS K7105(6.4)に準拠し、ヘーズメーター(スガ試験機株式会社製、型式:HGM-2)により、ヘーズ(曇価)を測定した。また、JIS K5600(5.9)に準拠し、テーバー磨耗試験機(東洋精機製作所社製、型式:ROTARY ABRASION TESTER)に磨耗輪 CALIBRASE(登録商標)CS-10F(TABER社製)を装着し、荷重500g下での500回転後のヘーズ(曇価)を測定し、試験後と試験前のヘーズ(曇価)差ΔH500を耐擦傷性とした。耐擦傷性の判定基準としては、ΔH500≦+10であれば合格と判定される。
JIS K5600(5.6)に準拠し、カミソリ刃を用いて、ハードコート被膜に1mm間隔で縦、横11本ずつ切れ目を入れて100個の碁盤目を作製し、セロテープ(登録商標)(ニチバン社製、CT24)をよく付着させた後、剥離テストを行った。膜が剥離せずに残存したマス目数(X)をX/100で表示した。
以下に示す耐候性試験を行った。すなわち、光源にメタルハライドランプを用いた促進耐候性試験機(ダイプラ・ウインテス製;ダイプラ・メタルウェザー「KW-R5TP-A」)を用い、光照射、結露、暗黒の3条件を連続で50サイクル(600時間)負荷した。
ここで、光照射の条件は、照度80mW/cm2(ウシオ電機株式会社製、商品名「UIT-101」で測定)、ブラックパネル温度63℃、相対湿度80%の条件下で4時間光を照射するものであり、結露の条件は、光を照射せずに相対湿度98%でブラックパネル温度を63℃から30℃に自然冷却させて4時間保持するものであり、暗黒の条件は、光を照射せずにブラックパネル温度75℃、相対湿度90%で4時間保持するものである。さらに、前記結露の前後にシャワーを各10秒ずつ実施する。
耐候性試験(50サイクル、600時間)後のハードコート被膜の外観を目視によって観察し、下記基準で異常の有無を判定した。
○:異常なし。
×:ハードコート被膜にクラック、剥離または著しいヘーズ有り。
JIS K5600(5.6)に準拠し、耐候性試験後のハードコート被膜にカミソリ刃を用いて1mm間隔で縦、横11本ずつ切れ目を入れて100個の碁盤目を作製し、セロテープ(登録商標)(ニチバン社製、CT24)をよく付着させた後、剥離テストを行った。ハードコート被膜が剥離せずに残存したマス目数をXとし、X/100で耐候密着性を表示した。
なお、2011年1月20日に出願された日本特許出願2011-009359号の明細書、特許請求の範囲、図面及び要約書の全内容をここに引用し、本発明の開示として取り入れるものである。
Claims (10)
- 樹脂基板の少なくとも一方の面上に、アクリル系ポリマー(P)およびシリル基含有アクリル系ポリマー(α)を主成分として含有するプライマー層、およびオルガノポリシロキサンの硬化物を主成分として含有するハードコート層を、前記樹脂基板側から順に有するハードコート被膜付き樹脂基板であって、
前記アクリル系ポリマー(P)は、炭素数1~6のアルキル基を有するメタクリル酸アルキルエステルに基づく重合単位から成り、該アクリル系ポリマー(P)を構成する重合単位全体の90~100モル%がメタクリル酸メチルに基づく重合単位であり、
前記シリル基含有アクリル系ポリマー(α)は、メタクリル酸メチル(MMA)に基づく重合単位、ならびに加水分解性シリル基および/またはSiOH基を有する重合単位を含有し、該シリル基含有アクリル系ポリマーを構成する重合単位全体の50~95モル%がメタクリル酸メチル(MMA)に基づく重合単位であり、前記シリル基含有アクリル系ポリマー(α)は、芳香族炭化水素基を側鎖に有する重合単位を含有せず、
前記アクリル系ポリマー(P)と前記シリル基含有アクリル系ポリマー(α)との質量比、すなわち(アクリル系ポリマー(P)の含有量)/(アクリル系ポリマー(P)の含有量とシリル基含有アクリル系ポリマー(α)の含有量との合計量)×100の値が、50~98質量%であることを特徴とするハードコート被膜付き樹脂基板。 - 前記シリル基含有アクリル系ポリマー(α)は、前記加水分解性シリル基および/またはSiOH基を有する重合単位を、該シリル基含有アクリル系ポリマー(α)を構成する重合単位全体の5~50モル%の割合で含有する、請求項1に記載のハードコート被膜付き樹脂基板。
- 前記シリル基含有アクリル系ポリマー(α)は、前記メタクリル酸メチル(MMA)に基づく重合単位、ならびに前記加水分解性シリル基および/またはSiOH基を有する重合単位から成り、前記メタクリル酸メチル(MMA)に基づく重合単位と、前記加水分解性シリル基および/またはSiOH基を有する重合単位とのモル比が、50:50~95:5である、請求項1または2に記載のハードコート被膜付き樹脂基板。
- 前記加水分解性シリル基および/またはSiOH基を有する重合単位が、3-メタクリロキシプロピルトリメトキシシラン、3-メタクリロキシプロピルメチルジメトキシシラン、3-メタクリロキシプロピルジメチルメトキシシラン、3-メタクリロキシプロピルトリエトキシシラン、3-メタクリロキシプロピルメチルジエトキシシラン、3-アクリロキシプロピルトリメトキシシランおよび3-アクリロキシプロピルメチルジメトキシシラン、ならびにこれらの加水分解物または部分加水分解物に基づく重合単位からなる群から選ばれる少なくとも1種である、請求項1~3のいずれか1項に記載のハードコート被膜付き樹脂基板。
- 前記シリル基含有アクリル系ポリマー(α)は、ヒドロキシアルキル基を有する重合単位を含有しない、請求項1~4のいずれか1項に記載のハードコート被膜付き樹脂基板。
- 前記アクリル系ポリマー(P)は、メタクリル酸メチルに基づく重合単位から成る、請求項1~5のいずれか1項に記載のハードコート被膜付き樹脂基板。
- 前記シリル基含有アクリル系ポリマー(α)の質量平均分子量は、5,000~300,000である、請求項1~6のいずれか1項に記載のハードコート被膜付き樹脂基板。
- 前記プライマー層の主成分である前記アクリル系ポリマー(P)の質量平均分子量は、20,000~1,500,000である、請求項1~7のいずれか1項に記載のハードコート被膜付き樹脂基板。
- 前記オルガノポリシロキサンはT単位とQ単位のみで構成され、その個数の割合は、T:Q=90~100:10~0である、請求項1~8のいずれか1項に記載のハードコート被膜付き樹脂基板。
- 樹脂基板の少なくとも一方の面上に、アクリル系ポリマー(P)およびシリル基含有アクリル系ポリマー(α)を主成分として含有するプライマー層形成用組成物を塗布し乾燥させてプライマー層を形成する工程と、前記プライマー層の上に、オルガノポリシロキサンを主成分として含有するハードコート層形成用組成物を塗布し硬化させてハードコート層を形成する工程と、を備えるハードコート被膜付き樹脂基板の製造方法であって、
前記アクリル系ポリマー(P)は、炭素数1~6のアルキル基を有するメタクリル酸アルキルエステルに基づく重合単位から成り、該アクリル系ポリマー(P)を構成する重合単位全体の90~100モル%がメタクリル酸メチルに基づく重合単位であり、
前記シリル基含有アクリル系ポリマー(α)は、メタクリル酸メチル(MMA)に基づく重合単位、ならびに加水分解性シリル基および/またはSiOH基を側鎖に有する重合単位を含有し、該シリル基含有アクリル系ポリマー(α)を構成する重合単位全体の50~95モル%がメタクリル酸メチル(MMA)に基づく重合単位であり、
前記シリル基含有アクリル系ポリマー(α)は、芳香族炭化水素基を側鎖に有する重合単位を含有せず、
前記アクリル系ポリマー(P)と前記シリル基含有アクリル系ポリマー(α)との質量比、すなわち(アクリル系ポリマー(P)の含有量)/(アクリル系ポリマー(P)の含有量とシリル基含有アクリル系ポリマー(α)の含有量との合計量)×100の値が、50~98質量%である、ことを特徴とするハードコート被膜付き樹脂基板の製造方法。
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CN109922871A (zh) * | 2016-08-16 | 2019-06-21 | 唐纳森公司 | 烃流体-水分离 |
WO2024024615A1 (ja) * | 2022-07-26 | 2024-02-01 | 信越化学工業株式会社 | プライマー組成物および被覆物品 |
US12017161B2 (en) | 2018-02-15 | 2024-06-25 | Donaldson Company, Inc. | Filter media configurations |
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US20150159036A1 (en) * | 2013-12-11 | 2015-06-11 | Momentive Performance Materials Inc. | Stable primer formulations and coatings with nano dispersion of modified metal oxides |
JP2016037046A (ja) * | 2014-08-06 | 2016-03-22 | 三菱樹脂株式会社 | 積層ポリエステルフィルム |
JP6465038B2 (ja) * | 2016-01-08 | 2019-02-06 | 信越化学工業株式会社 | 積層体およびその製造方法 |
KR102111875B1 (ko) * | 2016-03-23 | 2020-05-15 | 후지필름 가부시키가이샤 | 적층체, 패턴 형상 피도금층이 있는 기판의 제조 방법, 금속층 함유 적층체의 제조 방법, 터치 패널 센서, 및 터치 패널 |
US10634612B2 (en) * | 2016-07-19 | 2020-04-28 | Hp Indigo B.V. | Assessment of primer content on a print substrate |
JP7505410B2 (ja) * | 2018-12-13 | 2024-06-25 | セメダイン株式会社 | プライマー組成物 |
CN116285554B (zh) * | 2023-03-13 | 2023-09-29 | 华南农业大学 | 一种耐冲击的透明超疏水涂层的制备方法 |
KR102664602B1 (ko) * | 2023-08-14 | 2024-05-10 | 광주과학기술원 | 폴리카보네이트 기반 광학 적층체, 그 제조 방법 및 이를 이용한 커버윈도우 |
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