WO2013121697A1 - (メタ)アクリレート系樹脂組成物及びその硬化物 - Google Patents
(メタ)アクリレート系樹脂組成物及びその硬化物 Download PDFInfo
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- WO2013121697A1 WO2013121697A1 PCT/JP2013/000282 JP2013000282W WO2013121697A1 WO 2013121697 A1 WO2013121697 A1 WO 2013121697A1 JP 2013000282 W JP2013000282 W JP 2013000282W WO 2013121697 A1 WO2013121697 A1 WO 2013121697A1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
- C08K5/0025—Crosslinking or vulcanising agents; including accelerators
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/10—Esters; Ether-esters
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L33/00—Compositions 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; Compositions of derivatives of such polymers
- C08L33/04—Homopolymers or copolymers of esters
- C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
- C08L33/08—Homopolymers or copolymers of acrylic acid esters
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2312/00—Crosslinking
Definitions
- the present invention relates to a (meth) acrylate-based resin composition that can be suitably used as a substitute for a glass plate such as a window glass for vehicles or buildings, a cover for a solar battery panel, and a cured product thereof.
- (meth) acrylate resins represented by polymethyl methacrylate (PMMA) and the like are used to obtain various molded products by taking advantage of their excellent properties such as transparency, weather resistance, surface hardness, and chemical resistance. It is used as a raw material.
- PMMA polymethyl methacrylate
- acrylate resins since such a (meth) acrylate resin has a relatively low impact resistance, its use may be limited in a field where impact characteristics are required.
- thermoplastic polymer or a (meth) acrylic acid ester compound having a long alkyl chain length is added.
- thermoplastic polymer when added as described above, the impact characteristics are improved, but the viscosity is increased, so that the moldability of the (meth) acrylate resin may be greatly reduced.
- a long-chain alkyl group when introduced, flexibility is imparted and impact characteristics are improved, but heat resistance may be reduced.
- rubber such as acrylic rubber is blended, there is a problem that heat resistance is lowered and strength such as bending strength is also lowered.
- the present invention has been made in view of the above points, and a (meth) acrylate resin composition capable of imparting high impact characteristics to a molded product while maintaining excellent heat resistance and bending characteristics (bending strength). It aims at providing a thing and its hardened
- the (meth) acrylate resin composition according to the present invention includes a (meth) acrylic resin composition (A) containing (meth) acrylic acid ester and poly (meth) acrylic acid ester, and a bifunctional compound represented by [Chemical Formula 1].
- the (meth) acrylate-based resin composition comprises 2 to 25 parts by mass of the bifunctional (meth) acrylic monomer (C) with respect to 100 parts by mass of the (meth) acrylic resin composition (A). 0.1 to 5 parts by mass of the polyfunctional unsaturated ester compound (D) having 3 or more functional groups is contained.
- the (meth) acrylic ester is a monofunctional unsaturated (meth) acrylic ester, and the poly (meth) acrylic ester is the monofunctional. It is preferable to contain unsaturated (meth) acrylic acid ester as a structural unit.
- the cured product of the present invention is characterized by curing the above (meth) acrylate resin composition.
- the (meth) acrylate resin composition of the present invention contains a specific bifunctional (meth) acrylic monomer (C) as a crosslinking agent. Therefore, high impact characteristics can be imparted to molded articles obtained from this (meth) acrylate-based resin composition while maintaining excellent heat resistance and bending characteristics (bending strength).
- the cured product of the present invention is obtained by curing the above (meth) acrylate resin composition, it has high impact characteristics while maintaining excellent heat resistance and bending characteristics (bending strength). It is.
- the (meth) acrylate resin composition of the present invention comprises a (meth) acrylic resin composition (A) and a crosslinking agent (B).
- the (meth) acrylic resin composition (A) includes (meth) acrylic acid ester and poly (meth) acrylic acid ester.
- the crosslinking agent (B) contains at least a bifunctional (meth) acrylic monomer (C) represented by [Chemical Formula 1] and a polyfunctional unsaturated ester compound (D) having three or more radical polymerizable functional groups. It is composed.
- the (meth) acrylic resin composition (A), the crosslinking agent (B), the bifunctional (meth) acrylic monomer (C), and the radical polymerizable functional group in the (meth) acrylate resin composition of the present invention are three.
- the polyfunctional unsaturated ester compound (D) having the above will be described in detail.
- “(meth) acrylate” indicates either acrylate or methacrylate
- “(meth) acrylic acid ester” indicates either acrylic acid ester or methacrylic acid ester.
- (Meth) acrylic resin composition (A) contains (meth) acrylic acid ester and poly (meth) acrylic acid ester as described above.
- the (meth) acrylate resin composition of the present invention is prepared so as to be a base material in a molded product obtained by curing and molding the composition.
- Examples of the (meth) acrylic acid ester include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, (meth) Iso-butyl acrylate, tert-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, (meth) acrylic acid 3 -Hydroxypropyl, octyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, glycidyl (meth) acrylate, phenyl (meth) acrylate, phenoxy (meth) acrylate, 4-t-butyl Cyclohexyl (meth
- the (meth) acrylic acid ester it is preferable to use a monofunctional unsaturated (meth) acrylic acid ester as exemplified above. Therefore, in the embodiment of the present invention, it is preferable to use a single monofunctional unsaturated (meth) acrylic ester as the (meth) acrylic ester, or a monofunctional unsaturated (meth) in combination of two or more. It is preferable to use acrylic acid ester as (meth) acrylic acid ester.
- the monofunctional unsaturated (meth) acrylic acid ester means a (meth) acrylic acid ester having one (meth) acrylic group, that is, one vinyl group in its molecular structure.
- MMA methyl methacrylate
- the impact resistance of the cured product obtained from the (meth) acrylate resin composition is excellent. Furthermore, heat resistance and bending strength are not easily impaired, and the curability is excellent.
- the impact resistance of the cured product obtained from the (meth) acrylate resin composition is particularly excellent, and the heat resistance and bending strength are not easily impaired, and the curability is high. Even better.
- (Meth) acrylic resin composition (A) contains (meth) acrylic acid ester and poly (meth) acrylic acid ester as main components.
- This main component refers to the component contained in the (meth) acrylic resin composition (A).
- the main component is preferably contained in an amount of 80% by mass or more, more preferably 90% by mass or more based on the total mass of the (meth) acrylic resin composition (A).
- the said main component is good to contain at 100 mass% or less with respect to the total mass of a (meth) acrylic resin composition (A).
- the (meth) acrylic resin composition (A) contains 80% by mass or more of the main component composed of (meth) acrylic acid ester and poly (meth) acrylic acid ester, so that the methacrylic resin of the present invention.
- the cured product and molded product obtained from the composition can ensure transparency.
- a polymerizable monomer other than the (meth) acrylic acid ester examples thereof include styrene, ⁇ -methylstyrene, vinyl acetate, acrylamide and the like.
- the poly (meth) acrylic acid ester is a polymer obtained by polymerizing a (meth) acrylic acid ester monomer, and the (meth) acrylic acid ester monomer in this case is (meth) exemplified as described above. What is necessary is just the same as an acrylic ester.
- the poly (meth) acrylic acid ester is either a homopolymer composed of one (meth) acrylic acid ester monomer or a copolymer composed of two (meth) acrylic acid ester monomers. There may be.
- the poly (meth) acrylic acid ester may be a crosslinked or non-crosslinked polymer.
- poly (meth) acrylic acid ester when the poly (meth) acrylic acid ester is a copolymer, any polymer of a random copolymer, a block copolymer, an alternating copolymer, and a graft copolymer may be used. Moreover, if it is a grade which does not inhibit the effect of this invention, poly (meth) acrylic acid ester may also contain monomers other than (meth) acrylic acid ester monomer as a structural unit. Examples of monomers other than such (meth) acrylic acid ester monomers include monomer compounds such as styrene and vinyl acetate.
- the poly (meth) acrylic acid ester may include the monofunctional unsaturated (meth) acrylic acid ester as a structural unit.
- examples of the poly (meth) acrylic acid ester include a monofunctional (meth) acrylic acid ester polymerized material obtained by polymerizing a monofunctional unsaturated (meth) acrylic acid ester. This polymer has non-reactive groups in the side chain. In this case, non-reactive means the property that the group which monofunctional unsaturated (meth) acrylic ester has does not participate in the polymerization reaction at the time of obtaining monofunctional (meth) acrylic ester polymeric material.
- the monofunctional (meth) acrylic acid ester polymerized material is a homopolymer composed of one monofunctional unsaturated (meth) acrylic acid ester or two monofunctional unsaturated (meth) acrylic acid esters. Any of the copolymers comprised by these may be sufficient.
- the monofunctional (meth) acrylic acid ester polymerized material may be either a crosslinked or non-crosslinked polymer.
- the monofunctional (meth) acrylic acid ester polymerizing material is a copolymer, any polymer of a random copolymer, a block copolymer, an alternating copolymer, and a graft copolymer may be used.
- the monofunctional (meth) acrylic acid ester polymerized material may contain a monomer other than the monofunctional unsaturated (meth) acrylic acid ester as a constituent unit as long as the effect of the present invention is not impaired.
- monomers other than such monofunctional unsaturated (meth) acrylic acid esters include monomer compounds such as styrene and vinyl acetate.
- the (meth) acrylic resin composition (A) in the present invention contains a monofunctional unsaturated (meth) acrylic acid ester and a monofunctional (meth) acrylic acid ester polymerized material as main components.
- the main component refers to a component contained in the (meth) acrylic resin composition (A).
- Such a monofunctional (meth) acrylic acid ester polymerized material includes the above monofunctional unsaturated (meth) acrylic acid ester as a structural unit.
- Examples of such monofunctional (meth) acrylate polymerized materials include poly (meth) acrylate methyl, poly (meth) ethyl acrylate, poly (meth) acrylate butyl, and poly (meth) acrylate cyclohexyl. , Ethyl hexyl poly (meth) acrylate, lauryl poly (meth) acrylate, and the like.
- the (meth) acrylic acid esters exemplified above may be used alone or in combination of two or more.
- the content of the main component composed of the monofunctional unsaturated (meth) acrylic acid ester and the monofunctional (meth) acrylic acid ester polymerized material is based on the total amount of the (meth) acrylic resin composition (A). It is preferably 80% by mass or more, and more preferably 90% by mass or more. In this case, the content of the main component composed of the monofunctional unsaturated (meth) acrylic acid ester and the monofunctional (meth) acrylic acid ester polymerized material is 100 with respect to the total amount of the (meth) acrylic resin composition (A). It is good that it is less than mass%.
- the (meth) acrylic resin composition (A) is composed of (meth) acrylic ester and a monofunctional (meth) acrylic ester polymerized material as the main component of the (meth) acrylic resin composition (A).
- the transparency of a methacrylic resin composition is securable.
- (meth) acrylic resin composition (A) contains monofunctional unsaturated (meth) acrylic acid ester among monofunctional unsaturated (meth) acrylic acid ester and monofunctional (meth) acrylic acid ester polymerized material. May be.
- the (meth) acrylic resin composition (A) preferably contains a monofunctional unsaturated (meth) acrylic ester in the range of 30 to 95% by mass, and in the range of 60 to 85% by mass. More preferably.
- the (meth) acrylic resin composition (A) is a monofunctional (meth) acrylic acid ester polymerized material among monofunctional unsaturated (meth) acrylic acid esters and monofunctional (meth) acrylic acid ester polymerized materials. You may contain.
- the (meth) acrylic resin composition (A) preferably contains a monofunctional (meth) acrylic acid ester polymerized material in the range of 5 to 70% by mass, and in the range of 15 to 40% by mass. More preferably.
- the (meth) acrylic resin composition (A) can contain a polymerizable monomer as long as the effect of the present invention is not inhibited.
- This polymerizable monomer is a compound different from the monofunctional unsaturated (meth) acrylic acid ester and the monofunctional (meth) acrylic acid ester polymerized material. Examples of such a polymerizable monomer include styrene, ⁇ -methylstyrene, vinyl acetate, acrylamide and the like.
- the monofunctional (meth) acrylic acid ester polymerized material contains a polymerizable monomer
- this polymerizable monomer becomes a constituent unit of the monofunctional (meth) acrylic acid ester polymerized material.
- Such a monofunctional (meth) acrylic acid ester polymerized material may be either a crosslinked or non-crosslinked polymer.
- the monofunctional (meth) acrylic acid ester polymerization material is a copolymer, polymers such as a random copolymer, a block copolymer, an alternating copolymer, and a graft copolymer can be used.
- the (meth) acrylic resin composition (A) contains a polymerizable monomer as described above, the polymerization reaction with the crosslinking agent (B) described later is improved. That is, since the polymer matrix structure in the molded body and cured product obtained from the (meth) acrylic resin composition becomes dense, the polymer structure becomes more stable.
- poly (meth) acrylic acid ester those produced by various methods can be adopted.
- the production method include solution polymerization, emulsion polymerization, suspension polymerization, bulk polymerization, and dispersion. Although it is polymerization or the like, there is no particular limitation on its production method.
- the poly (meth) acrylic acid ester is preferably a monofunctional (meth) acrylic acid ester polymerized material, and is polymethyl methacrylate (hereinafter sometimes abbreviated as PMMA). Further preferred.
- the impact resistance of the cured product obtained from the (meth) acrylate resin composition is excellent, and Further, heat resistance and bending strength are not easily impaired, and the curability and moldability are excellent. Further, a cured product having high transparency can be obtained.
- the impact resistance of the cured product obtained from the (meth) acrylate-based resin composition is excellent, and heat resistance and bending strength are not easily impaired, It also has excellent curability and moldability.
- the said poly (meth) acrylic acid ester is PMMA, the transparency of the hardened
- the (meth) acrylic resin composition (A) preferably contains (meth) acrylic acid ester and poly (meth) acrylic acid ester.
- the (meth) acrylic acid ester is preferably a monofunctional unsaturated (meth) acrylic acid ester, and more preferably MMA.
- the poly (meth) acrylic acid ester is preferably a monofunctional (meth) acrylic acid ester polymerized material, and more preferably PMMA.
- the (meth) acrylic acid ester is preferably contained in the range of 30 to 95% by mass, more preferably 60 to 85% by mass, based on the total amount of the (meth) acrylic resin composition (A). It is preferable to contain in the range.
- the poly (meth) acrylic acid ester is preferably contained in the range of 5 to 70% by mass, more preferably 15 to 40% by mass with respect to the total amount of the (meth) acrylic resin composition (A). It is preferable that it is contained in a range.
- the (meth) acrylic resin composition (A) particularly preferably contains MMA and PMMA.
- MMA and PMMA are used in combination, the impact resistance of the cured product obtained from the (meth) acrylate-based resin composition becomes very excellent, and the bending strength is prevented from becoming too low.
- the saturated (meth) acrylic acid ester is preferably blended so as to be 30 to 95% by mass, more preferably 60 to 85% by mass with respect to the total amount of the (meth) acrylic resin composition (A).
- the monofunctional (meth) acrylic acid ester polymerized material is preferably contained in the range of 5 to 70% by mass, more preferably 15 to 40% by mass with respect to the total amount of the (meth) acrylic resin composition (A). It is preferable to contain in the range of%.
- the MMA is 30 to 95 with respect to the total amount of the (meth) acrylic resin composition (A). It is preferable to blend so that it may become the mass%, and also it is preferable that it is 60 to 85 mass%.
- the PMMA is preferably contained in the range of 5 to 70% by mass, more preferably in the range of 15 to 40% by mass with respect to the total amount of the (meth) acrylic resin composition (A). preferable.
- the (meth) acrylic resin composition (A) particularly preferably contains MMA and PMMA.
- MMA and PMMA are used in combination, the impact resistance of the cured product obtained from the (meth) acrylate-based resin composition becomes very excellent, and there is no possibility that the bending strength becomes too low.
- the crosslinking agent (B) used in the present invention contains at least a bifunctional (meth) acrylic monomer (C) represented by the following [Chemical Formula 1].
- the bifunctional (meth) acrylic monomer (C) is a compound having a radical polymerizable double bond at both ends via an alkylene glycol group or an alkylene group.
- the value of nxk is preferably 10-30.
- the bifunctional (meth) acrylic monomer (C) has a relatively long spacer site (R 1 site) in the molecule. Accordingly, the bifunctional (meth) acrylic monomer (C) becomes a flexible crosslinking agent.
- the bifunctional (meth) acrylic monomer (C) it is possible to simultaneously impart flexibility while forming a three-dimensional crosslinked structure in the cured product of the (meth) acrylate resin composition. Become.
- the bifunctional (meth) acrylic monomer (C) is configured to expand and contract at the spacer portion. Accordingly, a cured product or a molded body obtained from the (meth) acrylate resin composition can easily absorb and relax the applied impact. As a result, the cured product and the molded body have excellent impact resistance. And while giving a softness
- n ⁇ k is more preferably 10 to 28.
- the (meth) acrylate-based resin composition can easily impart particularly high impact characteristics (impact strength) to the cured product.
- the bifunctional (meth) acryl monomer (C) exemplified above may be used alone or in combination of two or more.
- the blending amount of the bifunctional (meth) acrylic monomer (C) is 2 to 25 parts by mass with respect to 100 parts by mass of the (meth) acrylic resin composition (A).
- the blending amount of the bifunctional (meth) acrylic monomer (C) is more preferably 5 to 22 parts by mass, particularly preferably 10 to 10 parts by mass with respect to 100 parts by mass of the (meth) acrylic resin composition (A). 20 parts by mass.
- the crosslinking agent (B) may further contain a polyfunctional unsaturated ester compound (D) having two or more radical polymerizable functional groups (excluding [Chemical Formula 1]).
- the crosslinking agent (B) may further contain a polyfunctional unsaturated ester compound (D).
- This polyfunctional unsaturated ester compound (D) is a compound having two or more radical polymerizable functional groups. Therefore, the polyfunctional unsaturated ester compound (D) described above is a compound different from the bifunctional (meth) acrylic monomer (C) represented by [Chemical Formula 1].
- the cured product obtained from the (meth) acrylic resin composition and the molded product have higher heat resistance, and the strength is not easily lowered.
- polyfunctional unsaturated ester compound (D) described above examples include trifunctional unsaturated esters such as trimethylolethane tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, and tetramethylolmethane tri (meth) acrylate. , Tetrafunctional unsaturated esters such as tetramethylolmethane tetra (meth) acrylate and dipropylene glycol di (meth) acrylate. Such polyfunctional unsaturated ester compounds (D) may be used alone or in combination of two or more.
- the polyfunctional unsaturated ester compound (D) has three radical polymerizable functional groups, or three or more.
- the heat resistance and strength of the cured product and molded product obtained from the (meth) acrylic resin composition can be further improved, and the curing reactivity of the (meth) acrylic resin composition can be increased.
- the polyfunctional unsaturated ester compound (D) is preferably in the range of 0.1 to 5.0 parts by weight with respect to 100 parts by weight of the (meth) acrylic resin composition (A), 3.0 to 5 More preferably, it is in the range of 0.0 part by mass.
- the moldability and heat resistance of the (meth) acrylic resin composition are improved.
- the content of the polyfunctional unsaturated ester compound (D) is less than 0.1 parts by mass, the curing time of the (meth) acrylic resin composition becomes long, and the resulting cured product or Since the heat resistance of a molded object also deteriorates, it is not preferable.
- content of the polyfunctional unsaturated ester compound (D) described above exceeds 5.0 parts by mass, the curing rate of the (meth) acrylic resin composition becomes too fast, and the resulting cured product or molded article Appearance defects such as voids occur.
- the crosslinking agent (B) may contain a polyfunctional vinyl aromatic compound in addition to the polyfunctional unsaturated ester compound (D) exemplified above.
- This polyfunctional vinyl aromatic compound is a compound having two or more radical polymerizable functional groups.
- the polyfunctional vinyl aromatic compound include compounds such as divinylbenzene and divinylnaphthalene. That is, the polyfunctional vinyl aromatic compound means a compound in which a plurality of vinyl groups are added to the acene compound.
- the (meth) acrylate resin composition of the present invention may contain a radical reactive polymerization initiator in order to accelerate the curing reaction.
- a radical reactive polymerization initiator is not particularly limited, and for example, known ones such as organic peroxides such as diacyl peroxides, peroxyketals, alkyl peresters and percarbonates, and azo compounds are used. can do.
- organic peroxides include benzoyl peroxide, t-butyl peroxybenzoate, lauryl peroxide, t-butyl peroxide, t-butyl peroxypivalate, t-butyl peroxyisopropyl carbonate, t- Butyl peroxyacetate, 2,2-t-butylperoxybutane, t-butylperoxy-3,3,5 trimethylhexanoate, di-t-butylperoxyhexahydroterephthalate, di- (3,3, 5-trimethylhexanoyl) peroxide, dilauroyl peroxide, dibenzoyl peroxide, 1,1-di- (t-butylperoxy) cyclohexane, 2,2-di- (t-amylperoxy) butane, 2,2-di- (4,4-di-t- (butylperoxy) cyclo Xyl) propane, t-butylper
- Such radical-reactive polymerization initiators may be used alone or in combination of two or more.
- the (meth) acrylic resin composition is cured using the radical-reactive polymerization initiator exemplified above, the (meth) acrylic resin composition is irradiated with light or ultraviolet light having a predetermined intensity, or at a predetermined temperature.
- the (meth) acrylic resin composition can be cured by heating.
- the 10-hour half-life temperature of the polymerization initiator contained in the (meth) acrylic resin composition is particularly limited. However, it may be appropriately selected depending on the curing reactivity and the like.
- the 10-hour half-life temperature is a known index, and means a temperature necessary for the polymerization initiator to decompose by heat and to reduce the concentration of the polymerization initiator after 10 hours to half of the initial value. .
- the polymerization initiator is decomposed by irradiating with light or ultraviolet light having a predetermined intensity suitable for the polymerization initiator.
- the compound contained in the (meth) acrylic resin composition is polymerized, and the (meth) acrylic resin composition is cured to obtain a molded body or a cured product.
- the blending amount of the polymerization initiator is not particularly limited, but may be 0.1 to 5 parts by mass with respect to 100 parts by mass of the (meth) acrylic resin composition (A), for example.
- the (meth) acrylate resin composition may contain other various additive materials as long as the effects of the present invention are not impaired.
- the (meth) acrylate resin composition may contain fillers such as silica fibers and silica particles, and inorganic ultraviolet shielding agents such as titanium oxide, zinc oxide, and cerium oxide to the extent that transparency is not impaired.
- the (meth) acrylate resin composition is composed of the light stabilizer, the antioxidant, the heat stabilizer, the antistatic agent, the heat ray reflective agent, the heat ray absorbent, the flame retardant, the lubricant, the pigment, the diluting solvent, etc. May be included.
- the (meth) acrylate resin composition contains a filler
- 10 to 200 parts by mass of filler is added to the (meth) acrylate resin composition with respect to 100 parts by mass of the (meth) acrylic resin composition (A). It is preferable to contain in a thing.
- the (meth) acrylate resin composition contains a filler, the generation of voids in the molded product or cured product obtained from the (meth) acrylate resin composition is suppressed, and the molded product or cured product The elastic modulus can be improved.
- the (meth) acrylate resin composition preferably contains silica.
- the refractive index of the (meth) acrylate resin composition is configured to be close to the refractive index of the (meth) acrylic resin composition (A). Therefore, in a molded body or a cured product obtained from the (meth) acrylate resin composition, the elastic modulus can be improved while ensuring transparency.
- the (meth) acrylate resin composition of the present invention is a (meth) acrylic resin composition (A), a cross-linking agent (B) containing a bifunctional (meth) acrylic monomer (C), and other additives as necessary.
- the additives to be prepared can be prepared by blending predetermined amounts respectively.
- the poly (meth) acrylic acid ester (for example, PMMA) contained in the (meth) acrylic resin composition (A) is dissolved in the (meth) acrylic acid ester (for example, MMA). It is preferable that it is in the state.
- the (meth) acrylate-based resin composition prepared as described above is poured into a mold, a resin mold, a glass mold, or the like, and heated in a specific temperature range under pressure or normal pressure.
- a cured product (which may be called a molded product) can be obtained.
- a (meth) acrylate resin composition is applied onto the mold and cured by heating, a film-like molded article can be obtained.
- the temperature at which the (meth) acrylate-based resin composition is heat-cured can be appropriately set according to the type and blending amount of each raw material, and can be performed at 40 to 100 ° C., for example.
- the cured product (molded product) obtained as described above is formed while being crosslinked by the bifunctional (meth) acrylic monomer (C) having an appropriate spacer length, the cured product is a three-dimensional crosslinked product. While having the structure, good flexibility can be imparted. Accordingly, the cured product and the molded product have excellent impact resistance. Furthermore, strength properties such as heat resistance and bending strength of the cured product and molded product are maintained. Of course, the cured product thus obtained also has high transparency and chemical resistance.
- the (meth) acrylate resin composition of the present invention is preferably configured such that a cured product obtained from the (meth) acrylate resin composition has a transmittance of 70% or more.
- the transmittance may be evaluated using a cured product formed to have a thickness of about 5 mm.
- the molded product obtained by curing the (meth) acrylate resin composition of the present invention has substitutes for glass plates such as window glass for automobiles and buildings, and covers for solar battery panels, particularly impact resistance. It can be suitably used for applications as required.
- the cured product (molded product) of the (meth) acrylate resin composition is obtained by pouring the (meth) acrylate resin composition prepared as described above into a mold and curing it at 75 ° C. for 1 hour. It was.
- Example 7 As the polyfunctional unsaturated ester compound (D), a cured product was obtained in the same manner as in Example 1 except that the amount of trimethylolpropane trimethacrylate was 3 parts by mass.
- Example 8 As the polyfunctional unsaturated ester compound (D), a cured product was obtained in the same manner as in Example 1 except that the amount of trimethylolpropane trimethacrylate was 5 parts by mass.
- Table 1 shows the blending conditions of each example and comparative example. Table 1 also shows k, m, n value, and k ⁇ n value in [Chemical Formula 1] of the bifunctional (meth) acrylic monomer (C).
- Table 1 shows the results of evaluating the heat resistance, bending strength, and impact strength of the cured products of Examples and Comparative Examples obtained as described above. Each evaluation was performed as follows.
- the heat resistance of the obtained cured product was evaluated based on the glass transition temperature.
- the glass transition temperature was measured in accordance with JIS K 7121 (ISO 3146: Determining of melting behavior (melting temperature or melting range) of semi-crystalline polymers).
- the bending strength (bending characteristics) of the obtained cured product was performed in accordance with JIS K 7171 (ISO 178: Plastics-Determination of flexure properties).
- the cured products of Examples 1 to 8 obtained from the (meth) acrylate resin composition of the present invention had a cured product obtained without using a bifunctional (meth) acrylic monomer ( Compared to Comparative Example 3), the impact resistance strength was high.
- the cured products of Examples 1 to 8 had higher heat resistance and no significant decrease in bending strength compared to the cured product of Comparative Example 3. Therefore, it can be seen that the (meth) acrylate resin composition of the present invention can impart high impact properties while imparting excellent heat resistance and bending properties (bending strength) to the cured product.
- the bifunctional (meth) acrylic monomer (C) satisfies the predetermined range of the value of n ⁇ k, when it is excessively blended, the impact strength is excellent as in the cured product of Comparative Example 6. In addition, the bending strength and heat resistance decreased, and the curing time tended to be longer than those of Examples 1-8.
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Abstract
Description
また、本発明の(メタ)アクリレート系樹脂組成物において、前記(メタ)アクリル酸エステルは、単官能不飽和(メタ)アクリル酸エステルであり、前記ポリ(メタ)アクリル酸エステルは、前記単官能不飽和(メタ)アクリル酸エステルを構成単位として含むことが好ましい。
[化1]に示すように、2官能(メタ)アクリルモノマー(C)は、アルキレングリコール基又はアルキレン基を介して、両末端にラジカル重合性の二重結合を有する化合物である。
(メタ)アクリル酸エステルとしてメタクリル酸メチル70質量部[化2]に、ポリ(メタ)アクリル酸エステルとしてポリメタクリル酸メチル30質量部[化3]を溶解させ、(メタ)アクリル樹脂組成物(A)を調製した。次いで、2官能(メタ)アクリルモノマー(C)として[化1]のポリエチレングリコールジメタクリレート(k=2、m=1、n=9;日油株式会社製)10質量部と、多官能不飽和エステル化合物(D)としてトリメチロールプロパントリメタクリレート[化4](表1では「TMPT」と表記)1.0質量部と、ラジカル重合開始剤としてジ-(3、5、5-トリメチルヘキサノイル)パーオキサイド(化薬アクゾ(株)のトリゴノックス36-C75)0.3質量部とを、(メタ)アクリル樹脂組成物に添加した。また、さらにフィラーとしてシリカ(平均粒径11μm)150質量部を添加することで、(メタ)アクリレート系樹脂組成物を得た。
2官能(メタ)アクリルモノマー(C)として、ポリエチレングリコールジメタクリレート(k=2、m=1、n=9)の代わりにポリエチレングリコールジメタクリレート(k=2、m=1、n=6)を使用したこと以外は実施例1と同様の方法で硬化物を得た。
2官能(メタ)アクリルモノマー(C)として、ポリエチレングリコールジメタクリレート(k=2、m=1、n=9)の代わりにポリエチレングリコールジメタクリレート(k=2、m=1、n=14)を使用したこと以外は実施例1と同様の方法で硬化物を得た。
2官能(メタ)アクリルモノマー(C)として、ポリエチレングリコールジメタクリレート(k=2、m=1、n=9)の配合量を3質量部としたこと以外は実施例1と同様の方法で硬化物を得た。
2官能(メタ)アクリルモノマー(C)として、ポリエチレングリコールジメタクリレート(k=2、m=1、n=9)の配合量を20質量部としたこと以外は実施例1と同様の方法で硬化物を得た。
2官能(メタ)アクリルモノマー(C)として、ポリエチレングリコールジメタクリレート(k=2、m=1、n=9)の代わりに1、10-デカンジメタクリレート(k=1、m=0、n=10)を使用したこと以外は実施例1と同様の方法で硬化物を得た。
多官能不飽和エステル化合物(D)として、トリメチロールプロパントリメタクリレートの配合量を3質量部としたこと以外は実施例1と同様の方法で硬化物を得た。
多官能不飽和エステル化合物(D)として、トリメチロールプロパントリメタクリレートの配合量を5質量部としたこと以外は実施例1と同様の方法で硬化物を得た。
2官能(メタ)アクリルモノマー(C)として、ポリエチレングリコールジメタクリレート(k=2、m=1、n=9)の代わりにエチレングリコールジメタクリレート(k=2、m=1、n=1)を使用したこと以外は実施例1と同様の方法で硬化物を得た。
2官能(メタ)アクリルモノマー(C)として、ポリエチレングリコールジメタクリレート(k=2、m=1、n=9)の代わりにポリテトラメチレングリコールジメタクリレート(k=4、m=1、n=9)を使用したこと以外は実施例1と同様の方法で硬化物を得た。
2官能(メタ)アクリルモノマー(C)を使用せずに硬化物を得たこと以外は実施例1と同様の方法で硬化物を得た。
多官能不飽和エステル化合物(D)であるトリメチロールプロパントリメタクリレートを配合しなかったこと以外は実施例1と同様の方法で硬化物を得た。
多官能不飽和エステル化合物(D)として、トリメチロールプロパントリメタクリレートの配合量を10質量部としたこと以外は実施例1と同様の方法で硬化物を得た。
2官能(メタ)アクリルモノマー(C)として、ポリエチレングリコールジメタクリレートの配合量を40質量部としたこと以外は実施例1と同様の方法で硬化物を得た。
上記のようにして得られた各実施例、比較例の硬化物について、耐熱性、曲げ強度及び衝撃強度を評価した結果を表1に示す。尚、各評価については以下のようにして行った。
得られた硬化物の耐熱性は、ガラス転移温度により評価を行った。ガラス転移温度の測定はJIS K 7121(ISO 3146:Determination of melting behaviour (melting temperature or melting range) of semi-crystalline polymers)に準拠して行った。
得られた硬化物の曲げ強度(曲げ特性)は、JIS K 7171(ISO 178:Plastics-Determination of flexural properties)に準拠して行った。
得られた硬化物の衝撃強度は、JIS K 7110(ISO 180:Plastics-Determination of Izod impact strength)に準拠して行った。
Claims (3)
- (メタ)アクリル酸エステル及びポリ(メタ)アクリル酸エステルを含む(メタ)アクリル樹脂組成物(A)と、[化1]に示す2官能(メタ)アクリルモノマー(C)とラジカル重合性官能基を3個以上有する多官能不飽和エステル化合物(D)とを含有する架橋剤(B)とを含んで成り、前記(メタ)アクリル樹脂組成物(A)100質量部に対して前記2官能(メタ)アクリルモノマー(C)を2~25質量部、前記ラジカル重合性官能基を3個以上有する多官能不飽和エステル化合物を0.1~5質量部含有することを特徴とする(メタ)アクリレート系樹脂組成物。
- 前記(メタ)アクリル酸エステルは、単官能不飽和(メタ)アクリル酸エステルであり、前記ポリ(メタ)アクリル酸エステルは、前記単官能不飽和(メタ)アクリル酸エステルを構成単位として含むことを特徴とする請求項1に記載の(メタ)アクリレート系樹脂組成物。
- 請求項1又は2に記載の(メタ)アクリレート系樹脂組成物を硬化させて成ることを特徴とする硬化物。
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US14/342,484 US20140243493A1 (en) | 2012-02-13 | 2013-01-22 | (meth) acrylate resin composition and cured product of same |
EP13748888.8A EP2740764A4 (en) | 2012-02-13 | 2013-01-22 | RESIN COMPOSITION (METH) ACRYLATE AND CURED PRODUCT USING THE SAME |
CN201380002932.3A CN103781842A (zh) | 2012-02-13 | 2013-01-22 | (甲基)丙烯酸酯系树脂组合物及其固化物 |
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EP (1) | EP2740764A4 (ja) |
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JPWO2017030176A1 (ja) * | 2015-08-20 | 2018-05-31 | 富士フイルム株式会社 | 投映システムおよび投映システムの中間像スクリーンの製造方法 |
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JP6892831B2 (ja) * | 2016-01-22 | 2021-06-23 | 住友化学株式会社 | 樹脂組成物、成形体及び成形体の製造方法 |
KR102564083B1 (ko) * | 2016-12-05 | 2023-08-08 | 알케마 인코포레이티드 | 개시제 블렌드 및 그러한 개시제 블렌드를 함유하는 3차원 인쇄에 유용한 광경화성 조성물 |
FR3083240A1 (fr) * | 2018-06-28 | 2020-01-03 | Schneider Electric Industries Sas | Materiau dielectrique, son procede de fabrication et ses utilisations |
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CN103781842A (zh) | 2014-05-07 |
US20140243493A1 (en) | 2014-08-28 |
EP2740764A4 (en) | 2014-09-17 |
JPWO2013121697A1 (ja) | 2015-05-11 |
EP2740764A1 (en) | 2014-06-11 |
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