KR102488416B1 - thermosetting composition - Google Patents

Abstract

Provided is a thermosetting composition in which the obtained cured product has no problems of deformation or coloration and also has excellent mechanical properties such as hardness and bending properties. The thermosetting composition of the present invention includes component (A), component (B) and component (D), and optionally component (C), in 100% by weight of the total amount of components (A) to (C), ( An ethylenically unsaturated group containing 20 to 60% by weight of component A, 80 to 40% by weight of component (B), and 0 to 40% by weight of component (C), and also contained in components (A) to (C) It contains 20-60 mol% of methacryloyl groups in 100 mol% of the total amount of. Component (A): A compound having an isocyanurate ring and having two or more (meth)acryloyl groups (B) component: A compound having two or more (meth)acryloyl groups, other than component (A) Compound (C) component: Compound (D) component having one ethylenically unsaturated group: Thermal polymerization initiator

Description

thermosetting composition

The present invention relates to a thermosetting composition, which can be particularly suitably used for producing a resin sheet, and the obtained resin sheet can be suitably used for a substrate for optics such as a liquid crystal display (LCD) and organic EL, and a transparent conductive film for a touch panel. It can be used suitably with the resin sheet for formation, and belongs to these technical fields.

In addition, in this specification, an acryloyl group or a methacryloyl group is represented by a (meth)acryloyl group, and an acrylate or methacrylate is represented by (meth)acrylate.

Recently, a touch panel-integrated liquid crystal display device or a touch panel-integrated organic EL display device is increasingly applied to mobile devices such as smart phones, tablet terminals, and car navigation systems.

Conventionally, as a transparent conductive thin film of a touch panel, conductive glass in which a thin film of indium tin oxide (hereinafter referred to as "ITO") is formed on glass is well known, but flexibility and workability are poor because the substrate is glass. Therefore, depending on the application, a transparent conductive sheet made of a polyethylene terephthalate sheet as a base material is used from the advantages of being excellent in flexibility, processability and impact resistance, and being lightweight.

On the other hand, since it is expected to contribute to thinness and weight reduction of touch panels, improvement of transmittance, and cost reduction of members, a cover-integrated touch panel in which a touch sensor such as ITO is directly formed on a cover glass, so-called OGS (One Glass Solution) Some are being hired. However, the OGS type has a problem that the touch panel becomes inoperable when the cover glass is cracked.

Then, as a material for a cover excellent in impact resistance, so-called OPS (One Plastic Solution) is proposed in which a touch sensor such as ITO is directly formed on a resin sheet. However, conventional acrylic resin or polycarbonate resin sheets have low surface hardness, so they are easily scratched, and also have insufficient toughness, and may crack due to impact force from the outside.

Patent Document 1 discloses a plastic member for forming a transparent conductive film obtained by photocuring a photocurable composition containing a bismethacrylate having an alicyclic backbone and a mercapto compound.

In Patent Document 2, a photocurable composition containing a multifunctional urethane (meth)acrylate having an alicyclic structure, a bifunctional (meth)acrylate having an alicyclic structure, and a photopolymerization initiator is photocured to obtain a thickness of 50 to 500 μm. A transparent resin molded body of is disclosed.

Japanese Unexamined Patent Publication No. 2002-161113 Japanese Unexamined Patent Publication No. 2007-56180

However, the plastic member described in Patent Literature 1 imparts appropriate toughness to a cured product by blending a mercapto compound, but has a problem that the pot life (pot life) of the composition is shortened, and the surface hardness There was also a problem that the scratch resistance was also lowered.

Moreover, since rigidity equivalent to the transparent resin molded object described in patent document 2 and glass could not be expressed, there existed a problem that the appearance problem arises in the heating process in a transparent conductive film or metal electrode formation process.

As described above, a resin sheet having satisfactory physical properties as a resin for OPS has not been found so far, and in particular, it is difficult to achieve both hardness and toughness, and the scratch resistance is also insufficient.

In the production of resin sheets, there are the case of using the photocurable composition as described above and the thermosetting composition, but they are used separately depending on the purpose or characteristics.

As a feature of the thermosetting composition, it can be produced by a simple device, and it is possible to simultaneously manufacture a plurality of sheets with one warming device, but when a conventional thermosetting composition is used, a resin sheet obtained by heating There was a problem of deformation or discoloration.

Moreover, also when the above photocurable composition was applied to a thermosetting composition, it had the same problem.

The inventors of the present invention found that the cured product to be obtained has no problems of deformation or coloring, and also has excellent mechanical properties such as hardness and bending properties, and is hard to crack and has excellent impact resistance when used in the production of a thermosetting composition, especially a resin sheet. , In order to find out a thermosetting composition with excellent surface properties such as surface hardness and scratch resistance, an intensive study was conducted.

As a result of intensive studies to solve the above problems, the inventors of the present invention found that a composition containing di(meth)acrylate having an isocyanurate ring and other polyfunctional (meth)acrylates can solve the above problems. found out and came to complete the present invention.

The present invention includes the following component (A), component (B) and component (D), and optionally the following component (C),

20 to 60% by weight of component (A), 80 to 40% by weight of component (B), and 0 to 40% by weight of component (C) in 100% by weight of the total amount of components (A) to (C), also

(A) to (C) containing 20 to 60 mol% of methacryloyl groups in 100 mol% of the total amount of ethylenically unsaturated groups contained in components

It relates to a thermosetting composition.

Component (A): A compound having an isocyanurate ring and two or more (meth)acryloyl groups

Component (B): A compound having two or more (meth)acryloyl groups, other than component (A)

(C) component: a compound having one ethylenically unsaturated group

(D) component: thermal polymerization initiator

Moreover, you may paraphrase as follows.

The thermosetting composition of the present invention includes the component (A), component (B) and component (D), and may contain the component (C),

(C) In the case of containing component, in 100% by weight of the total amount of components (A) to (C), 20 to 60% by weight of component (A), 80 to 40% by weight of component (B), and component in an amount exceeding 0% by weight to 40% by weight, and 20 to 60% by mole of a methacryloyl group in 100% by mole of the total amount of ethylenically unsaturated groups contained in components (A) to (C),

(C) In the case of not including component, 20 to 60% by weight of component (A) and 80 to 40% by weight of component (B) are included in 100% by weight of the total amount of component (A) and component (B), Further, 20 to 60 mol% of methacryloyl groups are included in 100 mol% of the total amount of ethylenically unsaturated groups contained in component (A) and component (B).

As component (A), a compound having an isocyanurate ring and having two (meth)acryloyl groups or/and a compound having an isocyanurate ring and having three (meth)acryloyl groups is preferable. Do.

As component (B), it is preferable to include di(meth)acrylate (B-1) having a linear alkylene group of 4 to 20 carbon atoms.

In addition, as component (B-1), 1,4-butanedioldi(meth)acrylate, 1,6-hexanedioldi(meth)acrylate and 1,9-nonanedioldi(meth)acrylate are selected from 1 or more types are preferable.

Moreover, as component (B), it is preferable to further include a compound having three or more (meth)acryloyl groups.

(A) - (C) It is preferable not to contain the compound which has a urethane bond as a component.

As a ratio of component (D), it is preferable to contain 0.1 to 5 parts by weight of component (D) with respect to 100 parts by weight of the total amount of components (A) to (C).

As physical properties of the cured product of the composition, the flexural modulus in a bending test is preferably 2.5 GPa or more, and the total light transmittance is preferably 90% or more.

As a composition of this invention, it is preferable to use as a thermosetting composition for resin sheet manufacture.

Moreover, it is preferable that the obtained resin sheet is 100 micrometers - 5 mm as thickness of hardened|cured material.

As a method for producing the resin sheet, a method in which the thermosetting composition of the present invention is poured into a molding mold composed of a base material, a base material for forming a weir, and a base material in this order and then heated is preferable.

Hereinafter, the present invention will be described in detail.

According to the composition of the present invention, the obtained cured product has no problems of deformation or coloration, and has excellent mechanical properties such as hardness and bending properties, and when used in the production of a resin sheet, it is hard to crack and has excellent impact resistance. It is excellent, and it becomes a thing with excellent surface physical properties such as surface hardness and scratch resistance.

[Brief Description of Drawings] [Brief Description of Drawings] [Brief Description of Drawings] Fig. 1 is a diagram showing an example of a molding die used when manufacturing a resin sheet using the composition of the present invention.

The present invention is a composition containing components (A) to (D),

20 to 60% by weight of component (A), 80 to 40% by weight of component (B), and 0 to 40% by weight of component (C) in 100% by weight of the total amount of components (A) to (C), also

(A) to (C) containing 20 to 60 mol% of methacryloyl groups in 100 mol% of the total amount of ethylenically unsaturated groups contained in components

It relates to a thermosetting composition.

Hereinafter, details of each component and composition are described.

1. Component (A)

(A) component is a compound which has an isocyanurate ring and has two or more (meth)acryloyl groups.

As component (A), various compounds can be used as long as they are compounds having an isocyanurate ring and having two or more (meth)acryloyl groups.

As component (A), a compound having an isocyanurate ring and having two (meth)acryloyl groups or/and a compound having three (meth)acryloyl groups is preferable.

Specific examples include di(meth)acrylate of an alkylene oxide adduct of isocyanurate, tri(meth)acrylate of an alkylene oxide of isocyanurate, and ε- for an alkylene oxide adduct of isocyanurate. di(meth)acrylate of caprolactone adduct, tri(meth)acrylate of epsilon-caprolactone adduct to isocyanuric acid alkylene oxide adduct, and the like.

Ethylene oxide, propylene oxide, etc. are mentioned as an alkylene oxide in an alkylene oxide adduct here, Ethylene oxide is preferable. As the added mole number of alkylene oxide, 1 to 3 moles are preferable in one molecule.

Moreover, as the number of moles of ε-caprolactone added, 1 to 3 moles are preferable in one molecule.

(A) As a component, only 1 type of said compound may be used, or you may use 2 or more types together.

(A) component is marketed, and the following products etc. are mentioned, for example.

Diacrylate of isocyanuric acid ethylene oxide 3 mole adduct: Aronix M-215 manufactured by Toa Synthesis Co., Ltd.

Triacrylate of 3 mole adducts of ethylene oxide isocyanurate: A-9300 manufactured by Shin-Nakamura Chemical Industry Co., Ltd., Pancryl FA-731A manufactured by Hitachi Chemical Co., Ltd.

A mixture of di and tri(meth)acrylates of 3 moles of isocyanuric acid ethylene oxide adduct: Aronix M-315 manufactured by Toa Synthesis Co., Ltd.

• Triacrylate of 1 mol of ε-caprolactone adduct to 3 mol of ethylene oxide isocyanurate: Shin-Nakamura Chemical Industry Co., Ltd. A-9300-1CL etc. are mentioned.

Triacrylate of 3 mol adduct of ε-caprolactone to 3 mol adduct of ethylene oxide isocyanurate: Aronix M-327 manufactured by Toa Synthesis Co., Ltd.

The content of component (A) is 20 to 60% by weight, preferably 30 to 55% by weight, of component (A) in 100% by weight of the total amount of components (A) to (C).

When the content of component (A) is less than 20% by weight, the fracture deformation and 50% impact fracture height are low, and the resin sheet becomes brittle, and when it exceeds 60% by weight, surface hardness and scratch resistance such as pencil hardness this deteriorates

2. (B) Component

(B) component is a compound which has two or more (meth)acryloyl groups, and is a compound other than (A) component.

As the component (B), a compound having two (meth)acryloyl groups [hereinafter referred to as "bifunctional (meth)acrylate"] and a compound having three or more (meth)acryloyl groups [hereinafter, "It is called a trifunctional (meth)acrylate"] etc. are mentioned.

2-1. Bifunctional (meth)acrylates

Examples of the bifunctional (meth)acrylate include di(meth)acrylate and polyalkylene glycol di(meth)acrylate having an alkylene group.

Preferred examples of the di(meth)acrylate having an alkylene group include di(meth)acrylate having a linear or branched alkylene group having 4 to 20 carbon atoms [hereinafter referred to as "component (B-1)"]. is preferable

Component (B-1) is a di(meth)acrylate having a linear or branched alkylene group having 4 to 20 carbon atoms. In the present invention, an alkylene group means a divalent substituent obtained by removing two hydrogen atoms from an alkane.

These di(meth)acrylates are excellent in hardness and scratch resistance of cured products compared to di(meth)acrylates having a linear or branched alkylene group having 3 or less carbon atoms, and are superior to compounds having 21 or more carbon atoms. , the cured product has excellent rigidity and heat resistance.

As the divalent linear alkylene group of 4 to 20 carbon atoms in component (B-1), a 1,4-butylene group, a 1,6-hexylene group or a 1,9-hexylene group having bonds at both ends. A nonylene group is preferred.

Specific examples of the compound include 1,4-butanedioldi(meth)acrylate, 1,6-hexanedioldi(meth)acrylate, and 1,9-nonanedioldi(meth)acrylate. .

As the divalent branched alkylene group having 4 to 20 carbon atoms in component (B-1), neopentylene group (2,2-dimethyl-1,3-propylene group) having bonds at both ends, 2- A methyl-1,3-propylene group and an isobutylene group having a degree of polymerization of 5 or less are preferred.

Specific examples of the compound include neopentyl glycol di(meth)acrylate, and it is most preferably used.

As the component (B-1), among these compounds, 1,4-butanedioldi(meth)acrylate, 1,6-hexanedioldi(meth)acrylate, 1,9-nonanedioldi(meth)acrylate And at least one selected from the group consisting of neopentyl glycol di(meth)acrylate is preferred.

As the component (B-1), among these compounds, at least one selected from the group consisting of 1,6-hexanedioldi(meth)acrylate and 1,9-nonanedioldi(meth)acrylate is further selected. more preferable

As the polyalkylene glycol di(meth)acrylate, a di(meth)acrylate having a total of 4 to 20 carbon atoms constituting the polyoxyalkylene group is preferable.

Specific examples of the polyalkylene glycol di(meth)acrylate include diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, polyethylene glycol di( Meth) acrylate, dipropylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, tetrapropylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, polybutylene glycol di (meth)acrylate and poly(1-methylbutylene glycol) di(meth)acrylate.

Among these compounds, polyalkylene glycol di(meth)acrylate is selected from the group consisting of polyethylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, and polybutylene glycol di(meth)acrylate. At least 1 type selected is preferable.

As the polyalkylene glycol di(meth)acrylate, among these compounds, at least one selected from the group consisting of polyethylene glycol di(meth)acrylate and polypropylene glycol di(meth)acrylate is more preferable. .

As bifunctional (meth)acrylates other than the above, bifunctional (meth)acrylates having aromatic skeletons such as di(meth)acrylates of bisphenol A alkylene oxide adducts and bisphenol A di(meth)acrylates;

bifunctional (meth)acrylates having aliphatic skeletons such as ethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, and neopentyl glycol di(meth)acrylate;

Hydroxy pivalic acid neopentyl glycol di(meth)acrylate;

bifunctional (meth)acrylates having alicyclic skeletons such as dimethylol tricyclodecane di(meth)acrylate, cyclohexane dimethanol di(meth)acrylate, and spiroglycol di(meth)acrylate;

Moreover, in the above, as an alkylene oxide adduct, an ethylene oxide adduct, a propylene oxide adduct, etc. are mentioned.

As a bifunctional (meth)acrylate, polyester (meth)acrylate, epoxy (meth)acrylate, polyether (meth)acrylate, etc. other than the compound mentioned above are mentioned.

Hereinafter, these compounds are demonstrated.

2-1-1. Polyester (meth)acrylate

As polyester (meth)acrylate, the dehydration condensate of polyester diol and (meth)acrylic acid, etc. are mentioned.

Here, as polyester diol, the reaction material of a diol, dicarboxylic acid, or its anhydride, etc. are mentioned.

As the diol, ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, polypropylene glycol, butylene glycol, polybutylene glycol, tetramethylene glycol, low molecular weight diols such as hexamethylene glycol, neopentyl glycol, cyclohexanedimethanol, 3-methyl-1,5-pentanediol, and 1,6-hexanediol; and alkylene oxide adducts of these compounds. .

As the dicarboxylic acid or its anhydride, dicarboxylic acids such as orthophthalic acid, isophthalic acid, terephthalic acid, adipic acid, succinic acid, fumaric acid, maleic acid, hexahydrophthalic acid, tetrahydrophthalic acid and trimellitic acid, and compounds thereof Anhydrides of , etc. are mentioned.

2-1-2. Epoxy (meth)acrylate

Epoxy (meth)acrylate is a compound obtained by an addition reaction of (meth)acrylic acid to an epoxy resin. As an epoxy resin, an aromatic epoxy resin, an aliphatic epoxy resin, etc. are mentioned.

As an aromatic epoxy resin, Specifically, Diglycidyl ether which has a benzene skeleton, such as resorcinol diglycidyl ether and hydroquinone diglycidyl ether; bisphenol-type diglycidyl ethers such as diglycidyl ether of bisphenol A, bisphenol F, bisphenol S, bisphenol fluorene or an alkylene oxide adduct thereof; novolac-type epoxy resins such as phenol novolak-type epoxy resins and cresol novolak-type epoxy resins; glycidyl phthalimide; And o-phthalic acid diglycidyl ester etc. are mentioned.

As an aliphatic epoxy resin, Specifically, Diglycidyl ether of alkylene glycol, such as ethylene glycol, propylene glycol, 1, 4- butanediol, and 1, 6- hexanediol; Diglycidyl ether of polyalkylene glycol, such as diglycidyl ether of polyethylene glycol and polypropylene glycol; diglycidyl ethers of neopentyl glycol, dibromoneopentyl glycol, and alkylene oxide adducts thereof; Diglycidyl ether of hydrogenated bisphenol A and its alkylene oxide adduct; And tetrahydrophthalic-acid diglycidyl ester etc. are mentioned.

In the above, as an alkylene oxide of an alkylene oxide adduct, ethylene oxide, a propylene oxide, etc. are preferable.

2-1-3. Polyether(meth)acrylate

Polyether (meth) acrylate oligomers include polyalkylene glycol (meth) diacrylate, polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, and polytetramethylene glycol di (meth) acrylate. ) Acrylate etc. are mentioned.

2-2. Trifunctional (meth)acrylate

As the trifunctional or higher functional (meth)acrylate, trimethylolpropane tri(meth)acrylate, pentaerythritol tri or tetra(meth)acrylate, ditrimethylolpropane tri or tetra(meth)acrylate, and dipentaeryth polyol poly(meth)acrylates such as litoltri, tetra, penta or hexa(meth)acrylate; And

Tri(meth)acrylate of trimethylolpropanealkylene oxide adduct, tri- or tetra(meth)acrylate of pentaerythritolalkylene oxide adduct, tri- or tetra(meth)acrylate of ditrimethylolpropanealkyleneoxide adduct, and poly(meth)acrylates of polyolalkylene oxide adducts such as tri, tetra, penta or hexa(meth)acrylates of dipentaerythritolalkylene oxide adducts.

In the poly(meth)acrylate of the above polyolalkylene oxide adduct, as the alkylene oxide, ethylene oxide and propylene oxide are preferable.

2-3. preferred mode

(B) As a component, only 1 type of said compound may be used, or you may use 2 or more types together.

As component (B), it is preferable to include the above-mentioned component (B-1), and as component (B-1), 1,4-butanedioldi(meth)acrylate and 1,6-hexanediol At least one selected from the group consisting of di(meth)acrylate and 1,9-nonanedioldi(meth)acrylate is preferred.

In this case, as a content rate of component (B-1), 30 to 70 weight% of component (B-1) is preferable in 100 weight% of the total amount of component (B).

Moreover, it is preferable that (B) component contains the compound which has 3 or more (meth)acryloyl groups.

In this case, as the content ratio of the compound having 3 or more (meth)acryloyl groups, 30 to 70% by weight of the compound having 3 or more (meth)acryloyl groups in 100% by weight of the total amount of the component (B) is preferable

2-4. content rate

The content of component (B) is 40 to 80% by weight, preferably 45 to 75% by weight, of component (B) in 100% by weight of the total amount of components (A) to (C).

When the content of component (B) is less than 40% by weight, surface hardness such as pencil hardness and scratch resistance are lowered, and when it exceeds 80% by weight, breaking deformation and 50% impact fracture height are low, and resin sheet becomes vulnerable

Moreover, as a preferable content rate of component (B-1), it is 30 to 70 weight% in 100 weight% of the total amount of (B) component.

3. (C) Component

(C) Component is a compound which has one ethylenically unsaturated group. Component (C) is a component blended for the purpose of adjusting the viscosity of the composition or adjusting various physical properties of the cured product according to the purpose.

(C) As an ethylenically unsaturated group in component, a (meth)acryloyl group, a vinyl group, a vinyl ether group, etc. are mentioned, A (meth)acryloyl group is preferable.

(C) As a component, the compound which has one (meth)acryloyl group [henceforth a "monofunctional (meth)acrylate"] etc. are mentioned.

Specific examples of the monofunctional (meth)acrylate include isobornyl (meth)acrylate, dicyclopentenyl (meth)acrylate, dicyclopentanyl (meth)acrylate, cyclohexyl (meth)acrylate, and trimethyl Cyclohexyl (meth)acrylate, 1-adamantyl (meth)acrylate, methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, n-butyl (meth)acrylate, i -Butyl (meth) acrylate, t-butyl (meth) acrylate, hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, 2-methoxyethyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, glycidyl (meth)acrylate, dimethylaminoethyl (meth)acrylate, diethylaminoethyl (meth)acrylate, benzyl (meth)acrylate, allyl (meth)acrylate, 2-ethoxyethyl (meth)acrylate, phenoxyethyl (meth)acrylate, o-phenylphenol ethylene oxide adduct (1 to 4 mole adduct) ( meth)acrylate, p-cumylphenolethylene oxide adduct (1 to 4 mole adduct) (meth)acrylate, phenyl (meth)acrylate, o-phenylphenyl (meth)acrylate, and p-cumylphenyl ( Meth) acrylate etc. are mentioned.

The monofunctional (meth)acrylate may be a compound having various functional groups.

Examples of the compound having a carboxyl group include (meth)acrylic acid, a polycaprolactone modified product of (meth)acrylic acid, a Michael addition type polymer of (meth)acrylic acid, and an adduct of 2-hydroxyethyl (meth)acrylate and phthalic anhydride. and carboxyl group-containing (meth)acrylates such as adducts of 2-hydroxyethyl (meth)acrylate and succinic anhydride.

Examples of the compound having a hydroxyl group include (meth)acrylates having a hydroxyl group.

Examples of the (meth)acrylate having a hydroxyl group include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, hydroxybutyl (meth)acrylate, and hydroxypentyl (meth)acrylate. , Hydroxyalkyl (meth)acrylates, such as hydroxyhexyl (meth)acrylate and hydroxyoctyl (meth)acrylate, etc. are mentioned.

Examples of the compound having an amide group include N-vinylformamide, N-vinylacetamide, N-vinylpyrrolidone, and (meth)acrylamide-based compounds.

Specific examples of the (meth)acrylamide-based compound include N-methyl (meth)acrylamide, N-ethyl (meth)acrylamide, N-isopropyl (meth)acrylamide, and N-t-butyl (meth)acrylamide. of N-alkylacrylamide;

N,N-dialkylacrylamides such as N,N-dimethyl(meth)acrylamide and N,N-diethyl(meth)acrylamide;

N-hydroxyethyl (meth)acrylamide, N-methylol (meth)acrylamide, N-methoxymethyl (meth)acrylamide and N-butoxymethyl (meth)acrylamide, N-methoxyethyl (meth)acrylamide ) N-alkoxyalkyl (meth)acrylamides such as acrylamide; And (meth)acryloyl morpholine etc. are mentioned.

Examples of the compound having a carbamate group include (meth)acrylate having an oxazolidone group, and specific examples include 2-(2-oxo-3-oxazolidinyl)ethyl acrylate and the like. can be heard

Examples of the compound having an imide group include compounds having a maleimide group. Examples of the compound having a maleimide group include (meth)acrylate having a hexahydrophthalimide group and (meth)acrylate having a tetrahydrophthalimide group. N-(meth)acryloyloxyethyl hexahydrophthalimide etc. are mentioned as a specific example of the (meth)acrylate which has a hexahydrophthalimide group. N-(meth)acryloyloxyethyl tetrahydrophthalimide etc. are mentioned as an example of the (meth)acrylate which has a tetrahydrophthalimide group.

(C) Examples of compounds other than monofunctional (meth)acrylates in component include aromatic vinyl compounds.

Styrene, alkyl styrene, halogenated styrene, etc. are mentioned as an aromatic vinyl compound.

Specific examples of alkyl styrene include methyl styrene, ethyl styrene and propyl styrene.

Specific examples of halogenated styrene include fluorostyrene, chlorostyrene, and bromostyrene.

As an aromatic vinyl compound, styrene is preferable among the above compounds.

(C) As a component, only 1 type of said compound may be used, or you may use 2 or more types together.

The content of component (C) is 0 to 40% by weight, preferably 0 to 20% by weight, of component (C) in 100% by weight of the total amount of components (A) to (C).

(C) When the content ratio of the component exceeds 40% by weight, since unreacted components remain in the resin sheet after curing, the resin sheet is plasticized and the flexural modulus decreases.

4. Ingredient (D)

(D) Component is a thermal polymerization initiator.

As component (D), various compounds can be used, and organic peroxides and azo-based initiators are preferable. Among these, organic peroxides are more preferable because they are excellent in polymerization initiator efficiency, can reduce outgas derived from decomposition products of polymerization initiators, and make the composition excellent in impact resistance.

Specific examples of the organic peroxide include 1,1-bis(t-butylperoxy)2-methylcyclohexane, 1,1-bis(t-hexylperoxy)-3,3,5-trimethylcyclohexane, 1 ,1-bis(t-hexylperoxy)cyclohexane, 1,1-bis(t-butylperoxy)-3,3,5-trimethylcyclohexane, 1,1-bis(t-butylperoxy)cyclo Hexane, 2,2-bis(4,4-di-butylperoxycyclohexyl)propane, 1,1-bis(t-butylperoxy)cyclododecane, dilauroyl peroxide, t-hexylperoxyiso Propyl monocarbonate, t-butylperoxymaleic acid, t-butylperoxy-3,5,5-trimethylhexanoate, t-butylperoxylaurate, t-butylperoxypivalate, t-hexylperoxy Pivalate, 2,5-dimethyl-2,5-di(m-toluylperoxy)hexane, t-butylperoxyisopropylmonocarbonate, t-butylperoxy2-ethylhexylmonocarbonate, t-hexylper Oxybenzoate, 2,5-dimethyl-2,5-di(benzoylperoxy)hexane, t-butylperoxyacetate, 2,2-bis(t-butylperoxy)butane, t-butylperoxybenzoate , n-butyl-4,4-bis(t-butylperoxy)valerate, di-t-butylperoxyisophthalate, α,α'-bis(t-butylperoxy)diisopropylbenzene, dicumylfer Oxide, 2,5-dimethyl-2,5-di(t-butylperoxy)hexane, t-butylcumyl peroxide, di-t-butyl peroxide, p-menthane hydroperoxide, 2,5-dimethyl- 2,5-di(t-butylperoxy)hexyn-3, diisopropylbenzene hydroperoxide, t-butyltrimethylsilyl peroxide, 1,1,3,3-tetramethylbutyl hydroperoxide, cumene hydroper oxide, t-hexyl hydroperoxide, t-butyl hydroperoxide, and the like.

Specific examples of the azo compound include 1,1'-azobis(cyclohexane-1-carbonitrile), 2-(carbamoyl azo)isobutyronitrile, and 2-phenylazo-4-methoxy-2. ,4-dimethylvaleronitrile, azodi-t-octane, and azodi-t-butane; and the like.

These may be used independently and may use 2 or more types together. Moreover, organic peroxide can also be made into a redox reaction by combining with a reducing agent.

As the content ratio of component (D), 0.1 to 5 parts by weight of component (D) is preferable with respect to 100 parts by weight of the total amount of components (A) to (C).

By setting the ratio of component (D) to 0.1 part by weight or more, the entire resin sheet can be uniformly cured, and by setting it to 5 parts by weight or less, outgas derived from the remaining low molecular weight polymerization initiator decomposition product can be reduced. .

5. Thermosetting composition

The present invention includes the above component (A), component (B) and component (D), and optionally the above component (C),

20 to 60% by weight of component (A), 80 to 40% by weight of component (B), and 0 to 40% by weight of component (C) in 100% by weight of the total amount of components (A) to (C), also

(A) to (C) containing 20 to 60 mol% of methacryloyl groups in 100 mol% of the total amount of ethylenically unsaturated groups contained in components

It relates to a thermosetting composition.

As the components (A) to (C), which are curable components cured by heating in the present invention, the above compounds can be appropriately combined and used, but it is preferable not to contain a compound having a urethane bond. A compound having a urethane bond, for example, a composition containing urethane (meth)acrylate causes coloring of the cured product.

The composition of the present invention needs to contain 20 to 60 mol% of methacryloyl groups, preferably 30 to 60 mol%, in 100 mol% of the total amount of ethylenically unsaturated groups contained in components (A) to (C). is mol%.

If the ratio of methacryloyl groups is less than 20 mol%, deformation of the resin sheet after thermal curing will increase, and if it exceeds 60 mol%, coloring before and after the heat resistance test will increase.

The ratio of methacryloyl groups in the present invention means mol% obtained by dividing the number of moles of all methacryloyl groups in components (A) to (C) by the number of moles of all ethylenically unsaturated groups and multiplying by 100. In addition, since the compound having two or more (meth)acryloyl groups is often a mixture of compounds having different numbers of (meth)acryloyl groups in commercial products, the ratio of (meth)acryloyl groups is inaccurate. There are cases. In this case, the (meth)acryloyl group equivalent of the raw material compound is measured in advance by iodine value or the like, and calculated based on this value.

As a method for producing the composition, it may be according to a conventional method, for example, by stirring and mixing component (A), component (B) and component (D), and, if necessary, component (C) and other components. can be manufactured

What is necessary is just to set the viscosity of a composition suitably according to the objective, and 50-10,000 mPa*s are preferable.

In addition, in this invention, a viscosity means the value measured at 25 degreeC using E-type viscometer.

The composition of the present invention has the above components (A), (B) and (D) as essential components, but various components such as (C) may be blended depending on the purpose.

As other components, specifically, an organic solvent, a plasticizer, a polymerization inhibitor or/and antioxidant, a light resistance improver, and a compound having two or more mercapto groups [hereafter referred to as "polyfunctional mercaptan"], etc. can be heard

Hereinafter, these components are explained. In addition, as for the component described later, only 1 type may be used, and 2 or more types may be used together.

5-1. other ingredients

1) organic solvent

The composition of the present invention may contain an organic solvent for the purpose of, for example, improving application properties to substrates.

However, when using the obtained resin sheet for a transparent conductive film use, it is preferable not to contain an organic solvent.

Specific examples of the organic solvent include hydrocarbon solvents such as n-hexane, benzene, toluene, xylene, ethylbenzene and cyclohexane;

Methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, isobutyl alcohol, 2-methoxyethanol, 2-ethoxyethanol, 2-(methoxymethoxy)ethanol, 2-isopropanol Poxyethanol, 2-butoxyethanol, 2-isopentyloxyethanol, 2-hexyloxyethanol, 2-phenoxyethanol, 2-benzyloxyethanol, furfuryl alcohol, tetrahydrofurfuryl alcohol, diethylene glycol, diethylene alcohol solvents such as glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, and propylene glycol monomethyl ether;

Tetrahydrofuran, dioxane, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, bis(2-methoxyethyl) ether, bis(2-ethoxyethyl) ether and bis(2-butoxy Ether type solvents, such as ethyl) ether;

Acetone, methyl ethyl ketone, methyl-n-propyl ketone, diethyl ketone, butyl methyl ketone, methyl isobutyl ketone, methylpentyl ketone, di-n-propyl ketone, diisobutyl ketone, phorone, isophorone, cyclopentanone ketone solvents such as cyclohexanone and methylcyclohexanone;

ester solvents such as ethyl acetate, butyl acetate, isobutyl acetate, methyl glycol acetate, propylene glycol monomethyl ether acetate, and cellosolve acetate; And

and aprotic polar solvents such as N,N-dimethylformamide, N,N-dimethylacetamide, dimethylsulfoxide, N-methyl-2-pyrrolidone, and γ-butyrolactone.

The proportion of the organic solvent may be appropriately set, but is preferably 90% by weight or less in the composition, and more preferably 80% by weight or less.

2) plasticizer

A plasticizer may be added for the purpose of imparting flexibility to the cured product and improving brittleness.

Specific examples of the plasticizer include phthalic acid dialkyl esters such as dioctyl phthalate and diisononyl phthalate, dialkyl esters of adipate such as dioctyl adipate, sebacic acid esters, azelaic acid esters, and phosphoric acids such as tricresyl phosphate. and liquid polyether polyols such as ester and polypropylene glycol, polycaprolactonediol, and liquid polyester polyols such as 3-methylpentanediol adipate. Moreover, soft acrylic polymers with a number average molecular weight of 10,000 or less are exemplified.

The blending ratio of these plasticizers may be appropriately set, but is preferably 30 parts by weight or less, more preferably 30 parts by weight or less relative to 100 parts by weight of the total of components (A) to (C) (hereinafter referred to as “curable component”). is 20 parts by weight or less.

By setting it as 30 parts by weight or less, it can be made excellent in strength and heat resistance.

3) Polymerization inhibitors or/and antioxidants

A polymerization inhibitor and/or antioxidant may be added to the composition of the present invention in order to improve storage stability.

As the polymerization inhibitor, hydroquinone, hydroquinone monomethyl ether, 2,6-di-tert-butyl-4-methylphenol, and various phenolic antioxidants are preferable, but sulfur-based secondary antioxidants and phosphorus-based secondary oxidation An inhibitor or the like may be added.

The total blending ratio of these polymerization inhibitors or/and antioxidants is preferably 3 parts by weight or less, more preferably 0.5 parts by weight or less with respect to 100 parts by weight of the total amount of the curable component.

4) Light fastness improver

To the composition of the present invention, a light fastness improver such as an ultraviolet absorber or a light stabilizer may be added.

As the ultraviolet absorber, 2-(2'-hydroxy-5-methylphenyl)benzotriazole, 2-(2'-hydroxy-3',5'-di-t-butylphenyl)benzotriazole, and 2 Benzotriazole compounds, such as -(2'-hydroxy-3'-t-butyl-5'-methylphenyl) benzotriazole;

triazine compounds such as 2,4-bis(2,4-dimethylphenyl)-6-(2-hydroxy-4-iso-octyloxyphenyl)-s-triazine;

2,4-dihydroxy-benzophenone, 2-hydroxy-4-methoxy-benzophenone, 2-hydroxy-4-methoxy-4'-methylbenzophenone, 2,2'-dihydroxy- 4-methoxybenzophenone, 2,4,4'-trihydroxybenzophenone, 2,2',4,4'-tetrahydroxybenzophenone, 2,3,4,4'-tetrahydroxybenzophenone Benzophenone compounds such as 2,3',4,4'-tetrahydroxybenzophenone, or 2,2'-dihydroxy-4,4'-dimethoxybenzophenone;

can be heard

As the light stabilizer, N,N'-bis(2,2,6,6-tetramethyl-4-piperidyl)-N,N'-diformylhexamethylenediamine, bis(1,2,6, 6-)pentamethyl-4-piperidyl)-2-(3,5-ditertbutyl-4-hydroxybenzyl)-2-n-butylmalonate, bis(1,2,2,6,6 - low molecular weight hindered amine compounds such as pentamethyl-4-piperidinyl) sebacate; N,N'-bis(2,2,6,6-tetramethyl-4-piperidyl)-N,N'-diformylhexamethylenediamine, bis(1,2,2,6,6-penta and hindered amine light stabilizers such as high molecular weight hindered amine compounds such as methyl-4-piperidinyl)sebacate.

The blending ratio of the light fastness improver is preferably 0 to 5 parts by weight, more preferably 0 to 1 part by weight, based on 100 parts by weight of the total amount of the curable component.

5) multifunctional mercaptans

Polyfunctional mercaptans can be incorporated as necessary for the purpose of preventing curing shrinkage of the cured composition or for the purpose of imparting toughness.

As the polyfunctional mercaptan, various compounds can be used as long as they are compounds having two or more mercapto groups.

For example, pentaerythritol tetrakithioglycolnate, pentaerythritol tetrakithiopropionate, etc. are mentioned.

The proportion of the polyfunctional mercaptan is preferably 20 parts by weight or less, more preferably 10 parts by weight or less, and particularly preferably 5 parts by weight or less with respect to 100 parts by weight of the curable component. By making this ratio into 20 parts weight or less, the heat resistance of the hardened|cured material obtained and the fall of rigidity can be prevented.

6) Other ingredients other than the above

In the composition of the present invention, in addition to the other components described above, a release agent, a filler, a soluble polymer, and the like can be blended.

The release agent is blended for the purpose of facilitating release of the obtained resin sheet from the base material. As the release agent, various surfactants can be used as long as they can be released from the substrate and the blended liquid and the cured product do not become cloudy. For example, anionic surfactants such as alkylbenzenesulfonic acid, cationic surfactants such as alkylammonium salts, nonionic surfactants such as polyoxyethylene alkyl ether, amphoteric surfactants such as alkylcarboxy betaines, and furthermore, fluorine and surfactants containing silicon.

The filler is blended for the purpose of improving the mechanical properties of the obtained resin sheet. As a filler, both an inorganic compound and an organic compound can be used. Silica, an alumina, etc. are mentioned as an inorganic compound. A polymer may be used as the organic compound. As a filler, when the resin sheet obtained from the composition of this invention is used for an optical use, what does not reduce optical properties is preferable.

A soluble polymer is blended for the purpose of improving the mechanical properties of the resulting resin sheet. A soluble polymer means a polymer that dissolves in a composition. In the present invention, a polymer insoluble in the composition is referred to as a filler and distinguished.

The blending ratio of these other compounds is preferably 20 parts by weight or less, and more preferably 10 parts by weight or less with respect to 100 parts by weight of the curable component.

5-2. Hardened material properties

The composition of the present invention exhibits an effect of not causing deformation of the cured product after thermal curing.

As a method of evaluating the physical property, a method of evaluating by means of an average value of in-plane retardation is preferable.

The average value of the in-plane retardation of the cured product of the present invention is preferably 10 nm or less, and more preferably 8 or less.

In the present invention, the in-plane retardation means a retardation generated in the X direction and the Y direction due to birefringence generated when linearly polarized light is incident on the resin sheet.

As physical properties of the cured product of the composition in the present invention, the flexural modulus in a bending test is preferably 2.5 GPa or more, more preferably 3.0 GPa or more. The hardened|cured material of a composition which has the said elastic modulus becomes a thing excellent in rigidity.

In addition, the modulus of elasticity in the bending test in the present invention means a value calculated from strains of 0.1% and 1% in a bending test conducted at a distance of 30 mm and a bending speed of 0.2 mm/min.

In the case of using the cured product of the composition of the present invention for optical applications, the total light transmittance is preferably 90% or higher, more preferably 91% or higher.

In addition, in this invention, total light transmittance means the result of measuring the test body of thickness 1mm based on JISK7375.

Moreover, as a physical property of the hardened|cured material of the composition in this invention, it is preferable that pencil hardness is 3H or more.

In addition, the pencil hardness in this invention means the value measured by the method according to JISK-5600.

5-3. film thickness

In the case of using the composition of the present invention for a resin sheet, the film thickness of the resin sheet may be appropriately set according to the purpose.

In particular, when used for glass replacement applications such as OPS, 100 μm to 5 mm is preferable, more preferably 200 μm to 3 mm, and particularly preferably 300 μm to 2 mm.

6. Usage

The composition of the present invention can be used for various purposes, and can be particularly suitably used as a molding material.

Examples of the molding material include a resin sheet and three-dimensional molding by an inkjet method, which can be suitably used for a resin sheet.

Hereinafter, a resin sheet is demonstrated.

6-1. Manufacturing method of resin sheet

As a resin sheet manufacturing method using the composition of this invention, various methods are employable, and the following 4 manufacturing methods are mentioned, for example.

1) Preparation 1

A method of applying a composition to a substrate and curing the composition by heating

2) Preparation 2

A method of applying a composition to a substrate, bonding it to another substrate, and then curing the composition by heating

3) Manufacturing method 3

A method of pouring a composition into a substrate having a space and curing the composition by heating

4) Manufacturing method 4

A method of pouring a composition into a substrate having a space and bonding it to another substrate, followed by heating to cure the composition

In the case where the resin sheet obtained from the composition of the present invention is used as a substitute for glass, the above production method 4 is preferable.

As the polymerization method, both a batch type and a continuous type can be employed.

Examples of the continuous method include a method in which a composition is coated or poured into a base material, and a belt-shaped base material is continuously supplied.

Another example of the continuous method is a method called a continuous casting method other than the above. That is, two continuous mirror-finished stainless steel belts are lined up and down in a caterpillar shape, the composition is poured between the belts, and polymerization is continuously performed between the belts while slowly moving the belts to prepare a resin sheet. how to do it, etc.

For glass replacement applications, batch mode is preferred.

6-1-1. write

As the base material, both a base material capable of being peeled off and a base material having no releasability (hereinafter referred to as "non-releasable base material") can be used.

Examples of the peelable substrate include metal, glass, a film subjected to release treatment, and a surface untreated film having peelability (hereinafter collectively referred to as "release material").

Examples of the release material include a silicone-treated polyethylene terephthalate film, a surface-untreated polyethylene terephthalate film, a surface-untreated cycloolefin polymer film, and a surface-untreated OPP film (polypropylene).

In order to make the resin sheet obtained from the composition of the present invention low in haze or impart surface smoothness, it is preferable to use a substrate having a surface roughness (center line average roughness) Ra of 0.15 μm or less as a peelable substrate, and 0.001 to 0.100 μm. A phosphorus substrate is more preferred. Moreover, as a haze, 3.0 % or less is preferable.

Specific examples of the substrate include glass, untreated surface polyethylene terephthalate film, and untreated surface OPP film (polypropylene).

In addition, in this invention, surface roughness Ra means what measured the unevenness of the surface of a film, and calculated the average roughness.

Examples of the non-releasable substrate include various plastics other than those described above, polyvinyl alcohol, cellulose acetate resins such as triacetyl cellulose and diacetyl cellulose, acrylic resins, polyesters, polycarbonates, polyarylates, polyethersulfones, Cyclic polyolefin resin etc. which use cyclic olefins, such as norbornene, as a monomer are mentioned.

As the substrate having a space portion, a substrate having a concave portion is exemplified. What formed a recessed part by drilling a hole of a predetermined shape made into the target film thickness into a release material is mentioned.

In this case, after pouring the composition into a substrate having a concave portion, another substrate may be overlapped on the substrate having the concave portion.

As another example of the base material having a space portion, one in which a weir (spacer) is formed on a mold release material so that the cured product has a target film thickness (hereinafter referred to as a "molding mold"), etc. can be mentioned. Also in this case, another substrate may be superimposed on the embankment.

As the release material in this case, glass and glass subjected to release treatment are preferable.

As an example of a molding die, FIG. 1 is taken and demonstrated.

1 (a1-1) and (a1-2) are two substrates [FIG. 1: (1) of (a1-1) and (1)' of (a1-2)], two sheets are excellent in releasability Substrate [Fig. 1: (2) of (a1-1) and (2)' of (a1-2)] and a substrate for forming one weir [Fig. 1: (3) of (a1-1)] This is an example of the forming mold that is configured.

1 (a2) shows two substrates [FIG. 1: (1) and (1)' in (a2)], and one substrate for forming a weir [FIG. 1: (3) in (a2)] It is an example of a molding type composed of.

As shown in Fig. 1, the base material for forming the weir [Fig. 1: (a1-1) (3)] is preferably of a shape having a hollow part for injecting the composition thereon [Fig. 1: (a1) -1) of (3-1)]. As the base material for forming the weir, various materials can be used, and silicone rubber and the like are exemplified.

Specific examples of (a1-1) and (a1-2) in FIG. 1 include a molding die composed of two sheets of glass as substrates, two sheets of release-treated films, and one substrate for forming weirs. .

Substrate for overlapping a release-treated film [Fig. 1: (2) of (a1-1)] on glass [Fig. 1: (1) of (a1-1)] and forming a weir thereon [Fig. 1 : (3) of (a1-1)] is overlapped to form a weir (spacer). Further, a release-treated film [Fig. 1: (2)' of (a1-2)] was overlaid thereon, and glass [Fig. 1: (1)' of (a1-2)] was overlaid thereon to form a molding die. do.

As a specific example of Fig. 1 (a2), as the base material [Fig. 1: (1) and (1)' of (a2)], glass or metal subjected to release treatment is used, and since the cured product has excellent releasability, , the two films subjected to the release treatment in (a1-1) or (a1-2) of Fig. 1 are not necessary.

Further, when the cured product itself of the composition is excellent in releasability, glass can also be used as the substrate [(1) and (1)' in Fig. 1 (a2)]. An example in which the cured product of the composition itself has excellent releasability is an example in which a release agent is blended with the composition.

6-1-2. Pretreatment of the composition

In the application or injection of the composition of the present invention, the composition is obtained by stirring and mixing the raw material components in order to prevent the inclusion of foreign matter or the occurrence of defects such as voids in the resulting resin sheet, or to have excellent optical properties. After that, it is preferable to use the purified one.

As a method for purifying the composition, a method for filtering the composition is convenient and preferable. Pressure filtration etc. are mentioned as a method of filtration.

The filtration accuracy is preferably 10 μm or less, more preferably 5 μm or less. The filtration precision is so preferable that it is small. From the viewpoints of filter clogging suppression, filter replacement frequency suppression, and productivity, the lower limit is preferably 0.1 µm.

In the manufacture of the resin sheet, in order to prevent air bubbles from being contained in the cured product, it is preferable to carry out a defoaming treatment after blending the respective components.

As a method of defoaming treatment, defoaming by stationary, vacuum decompression, centrifugal separation, cyclone (autorotation/revolution mixer), gas-liquid separation membrane, ultrasonic wave, pressure vibration, multi-screw extruder, etc. are mentioned.

6-1-3. application or injection

The coating method in the case of applying the composition to the substrate may be appropriately set according to the purpose, and conventionally known bar coaters, applicators, doctor blades, knife coaters, comma coaters, reverse roll coaters, die coaters, lip coaters, and gravure coaters and a method of applying with a micro gravure coater or the like.

In the case of injecting the composition into a substrate having a space, a method of inserting the composition into an injection device or an injection device such as a syringe and injecting the composition may be used.

The film thickness in this case may be appropriately set according to the target film thickness of the resin sheet described above.

In particular, when used for glass replacement applications, preferably for OPS applications, 100 μm to 5 mm is preferable, more preferably 200 μm to 3 mm, and particularly preferably 300 μm to 2 mm.

6-1-4. heating

As a heating method in the case of using a thermosetting composition as a composition, a method of immersing in a heat medium bath such as heat and oil, a method of using a hot press, and a method of holding in a thermostat type thermostat are exemplified.

Conditions such as heating temperature in the case of heating may be appropriately set depending on the composition, base material and purpose to be used. As heating temperature, 40-250 degreeC is preferable. What is necessary is just to set heating time suitably according to the composition used, the target resin sheet, etc., and 3 hours or more is mentioned. The upper limit of the heating time is preferably 24 hours or less in consideration of economy.

Moreover, heating temperature can also be changed according to a purpose. For example, when thermal polymerization initiators with different decomposition temperatures are used, and when curing deformation of the resulting resin sheet is eliminated, and the like.

Specific examples of the temperature include a method of polymerization at a relatively low temperature of about 40 to 80°C for several minutes to several hours and then polymerization at a relatively high temperature of 100°C or higher for several hours. According to the heating method, the curing deformation of the obtained resin sheet can be eliminated, and a resin sheet excellent in various mechanical properties such as fracture deformation can be obtained.

6-2. Uses of Resin Sheets

The resin sheet produced from the composition of the present invention can be particularly suitably used as an optical sheet.

An optical sheet formed from the composition of the present invention can be used for various optical applications. More specifically, a polarizer protective film for a polarizing plate, a support film for a prism sheet, and a sheet used for a liquid crystal display device such as a light guide film or a touch panel-integrated liquid crystal display device, various functional films (e.g., hard coat sheet, decorative sheet , transparent conductive sheet) and surface-shaped sheet (eg, moth-eye type antireflection sheet or sheet with a textured structure for solar cells) base sheet, outdoor light-resistant (weather-resistant) sheet for solar cells, etc., LED lighting/organic EL Uses, such as a film for lighting and a transparent heat-resistant sheet for flexible electronics, are mentioned.

Since the optical sheet formed from the composition of the present invention has excellent heat resistance, it can be suitably used for production of a transparent conductive sheet. As the composition used in this application, a non-solvent type composition containing no organic solvent is preferable from the viewpoint of being able to suppress generation of outgassing at the time of vacuum film formation of the transparent conductor layer.

Further, since the optical sheet of the present invention has excellent heat resistance, flexibility, and high strength even when it is a thick film, it can also be used as a transparent conductive sheet base material for OPS. In this case, an optical sheet having a film thickness of 0.5 mm or more and 1.5 mm or less It can be used more preferably.

The manufacturing method of a transparent conductive sheet may follow a conventional method.

As the metal oxide forming the transparent conductor layer, indium oxide, tin oxide, zinc oxide, titanium oxide, indium-tin composite oxide, tin-antimony composite oxide, zinc-aluminum composite oxide, indium-zinc composite oxide, titanium-niobium Complex oxides etc. are mentioned. Among these, from the viewpoint of environmental stability and circuit workability, indium-tin composite oxide and indium-zinc composite oxide are preferred.

As a method of forming the transparent conductor layer, a conventional method may be used, and a method of forming by a sputtering method using the optical sheet of the present invention, using the metal oxide and using a vacuum film forming apparatus, and the like may be cited. .

More specifically, after dehydration and degassing using the above metal oxide as a target material, evacuation is performed to achieve vacuum, the optical sheet is brought to a predetermined temperature, and then a transparent conductor layer is formed on the optical sheet using a sputtering device. and the like.

Example

Examples and comparative examples are shown below to explain the present invention more specifically.

In addition, "part" means a weight part below, and "%" means weight%.

1. Example 1 to Example 3, Comparative Example 1 to Comparative Example 3

1) Preparation of thermosetting composition

Components (A), (B) and (D) shown in Tables 1 and 2 below were blended in proportions shown in Tables 1 and 2 below, and after mixing with stirring, defoaming was performed under vacuum.

In addition, in the following description, the ratio of methacryloyl groups in 100 mol% of the total amount of ethylenically unsaturated groups is expressed as "methacryl ratio".

In addition, the symbol in Table 1 and Table 2 means the following.

(A) component

M-315: Di and triacrylate of isocyanuric acid ethylene oxide adduct, Aronix M-315 manufactured by Toa Synthesis Co., Ltd.

(B) component

NDDA: 1,9-nonanediacrylate, Viscot #260 manufactured by Osaka Organic Chemical Industry Co., Ltd.

NDDMA: 1,9-nonanedimethacrylate, NOD-N manufactured by Shin-Nakamura Chemical Industry Co., Ltd.

TMP-MA: Trimethylolpropane trimethacrylate, manufactured by Kyoeisha Chemical Co., Ltd., "Light Ester TMP"

M-309: Trimethylolpropane triacrylate, Aronix M-309 manufactured by Toa Synthesis Co., Ltd.

(D) component

BPO: t-butylperoxy-2-ethylhexanoate, Nichiyu Co., Ltd. Perbutyl O

2) Preparation of resin sheet

As a molding die for producing a resin sheet, a molding die shown in Fig. 1 (a2) was used.

Two glass plates [80 mm x 80 mm, thickness 3 mm] and one silicon plate (thickness 1.0 mm) were used. In addition, the thing which performed the mold release process with the silicon type compound was used for the glass plate.

A silicon plate [Fig. 1 (a2): (3)] was stacked on a glass plate [Fig. 1 (a2): (1)] to form a weir (spacer). Further, a glass plate [Fig. 1 (a2): (1)'] was overlaid thereon to form a molding die.

The composition obtained above was injected into the hollow portion of the molded silicon plate [Fig. 1 (a2): (3-1)] with a syringe.

The molding die was installed in a drying furnace, and after heating at 60°C for 0.5 hour, the temperature was raised to 120°C (heating rate: 10°C/hour) over 6 hours to cure the composition.

After cooling to room temperature, the glass was removed and demolded from the molding die to obtain a resin sheet.

3) Evaluation method

About the obtained resin sheet, the average of in-plane retardation, yellow index, flexural modulus, total light transmittance, drop test, and pencil hardness were evaluated according to the following method. Those results are shown in Table 1 and Table 2.

(1) Average of in-plane retardation

Using the obtained resin sheet, the in-plane retardation was measured with a polarization measuring system (KAMAIRI, manufactured by Fortron), and the retardation in the central portion excluding 5 mm from the end was measured to obtain an average value.

(2) Yellow index: Y.I.

In accordance with JIS K7375, the yellow index (Y.I.) of the resin sheet before and after heating at 230°C in air for 4 hours was measured at a thickness of 1 mm.

(3) Flexural modulus

Five test pieces with a length of 40 (mm) × a width of 10 (mm) were cut out from a resin sheet having a size of 80 mm × 80 mm and a thickness of 1 mm. , 50% RH), a three-point bending test was conducted. The average value of 5 test pieces was taken as the flexural modulus (GPa).

In addition, when yielding was observed and the fracture occurred at a strain of 1.2 times or more of the strain at which the stress was maximum, the fracture mode was defined as ductile fracture, and less than that, as brittle fracture.

(4) Total light transmittance

In accordance with JIS K7375, the total light transmittance of a resin sheet having a thickness of 1 mm was measured.

(5) Drop test (50% impact fracture height)

A test piece of length 60 (mm) x width 60 (mm) was cut out from the obtained resin sheet, and the obtained resin sheet was placed on a metal ring with a diameter of 50 mm in accordance with JIS K7211-1, and a tip diameter of 5 mm A conical weight having a weight of 40 g was dropped from a predetermined height to the central portion of the resin molded body, and the height at which the probability of breaking was 50% or more was recorded. The number of tests at each height was set to 10.

(6) pencil hardness

Based on JIS K-5600, the hardness of the surface of the obtained resin sheet was measured.

2. Comparative Example 4 to Comparative Example 9

1) Preparation of photocurable composition

2-hydroxy-2-methyl-1-phenyl-propan-1-one [BASF Japan Co., Ltd. Manufacture Darocure 1173. Hereinafter referred to as "DC1173"] were blended in the proportions shown in Tables 3 and 4 below, and after stirring and mixing, defoaming was performed under vacuum.

In addition, the abbreviation in Table 3 and Table 4 means the following except what was defined above.

(B) component

DCP-A: Dimethylol tricyclodecane diacrylate, manufactured by Kyoeisha Chemical Co., Ltd., light acrylate DCP-A

HBUA: Adduct of hexamethylene diisocyanate trimer and hydroxybutyl acrylate

2) Preparation of resin sheet

As a molding die for producing a resin sheet, a molding die shown in Fig. 1 (a2) was used.

The composition obtained above was injected into the hollow portion of the molded silicon plate [Fig. 1 (a2): (3-1)] with a syringe.

For the obtained molding die, from one side of the glass plate side, using an ultraviolet irradiation device (high pressure mercury lamp) manufactured by Eye Graphics Co., Ltd., an illuminance of 130 mW/cm 2 (UV-A, manufactured by Fusion UV Systems Japan Co., Ltd.) UV POWER PUCK) and exposed 20 times at a conveyor speed of 5 m/min. At this time, the irradiated surface was reversed for each exposure.

After standing to cool, the glass was removed from the molding die, and the obtained cured product was heated at 150°C for 16 hours to obtain a resin sheet.

3) Evaluation method

About the obtained resin sheet, the average of in-plane retardation, yellow index, flexural modulus, total light transmittance, drop test, and pencil hardness were evaluated in the same method as the above. Their results are shown in Table 3 and Table 4.

3. Comparative Example 10 and Comparative Example 11

1) Evaluation of commercially available resin sheets

Commercially available polymethyl methacrylate [Acrylite L manufactured by Mitsubishi Rayon Co., Ltd., hereinafter referred to as "PMMA"] and polycarbonate [Eupiron NF-2000 manufactured by Mitsubishi Gas Chemical Co., Ltd.]. Hereinafter referred to as "PC"] was used, and the average in-plane retardation, yellow index, flexural modulus, total light transmittance, drop test, and pencil hardness were evaluated according to the same method as above. Their results are shown in Table 5.

4. Overall

In the compositions of Examples 1 to 3, the resulting resin sheets were excellent in terms of average in-plane retardation, yellow index, flexural modulus, drop test, total light transmittance, and hardness.

In contrast, in Comparative Examples 1 to 3, which are heat-curable compositions containing components (A), (B) and (D), but do not contain methacrylate (the methacrylic ratio is less than 20 mol%), In the composition, the average of the in-plane retardation increased, that is, the resin sheet was deformed.

Further, the compositions of Comparative Examples 4 to 6 containing components (A) and (B), but which are photocurable compositions and do not contain methacrylate (the methacrylic ratio is less than 20 mol%), The average of the in-plane retardation increased, and the initial Y.I. value increased. The composition of Comparative Example 7, which is a photocurable composition, including components (A) and (B) and having a methacrylic ratio that satisfies the scope of the present invention, has a lowered average in-plane retardation, and Y.I. the value of has risen

Further, in the compositions of Comparative Examples 8 and 9, which do not contain (A), are photocurable compositions, and do not contain methacrylate (methacrylic ratio is less than 20 mol%), the average in-plane retardation increases. After doing so, the Y.I. value after the initial stage and the heating test has risen. In particular, the Y.I. value of the composition of Comparative Example 9 containing urethane acrylate increased significantly in the initial stage and after the heating test.

In addition, in Comparative Example 10 related to commercially available PMMA, the result of the drop test was degraded. Moreover, in Comparative Example 11 regarding commercially available PC, the average of the in-plane retardation was greatly increased.

The composition of the present invention can be used for various purposes, and can be particularly suitably used for production of resin sheets.

The obtained resin sheet can be used for various uses and can be suitably used as an optical sheet. The said optical sheet can be used suitably for manufacture of a transparent conductive sheet, and can be used suitably by manufacture of the transparent conductive sheet for touch panels.

Claims (13)

Comprising the following component (A), component (B) and component (D), and optionally the following component (C),
20 to 60% by weight of component (A), 80 to 40% by weight of component (B), and 0 to 40% by weight of component (C) in 100% by weight of the total amount of components (A) to (C), also
A thermosetting composition containing 20 to 60 mol% of methacryloyl groups in 100 mol% of the total amount of ethylenically unsaturated groups contained in components (A) to (C).
Component (A): A compound having an isocyanurate ring and two or more (meth)acryloyl groups
Component (B): Di(meth)acrylate having a linear or branched alkylene group having 4 to 20 carbon atoms, which is a compound other than component (A) as a compound having two or more (meth)acryloyl groups ( Compounds containing B-1)
(C) component: a compound having one ethylenically unsaturated group
(D) component: thermal polymerization initiator According to claim 1,
Column in which the component (A) is a compound having an isocyanurate ring and two (meth)acryloyl groups or/and a compound having an isocyanurate ring and three (meth)acryloyl groups curable composition. According to claim 1,
A thermosetting composition in which the component (B) contains di(meth)acrylate (B-1) having a linear alkylene group of 4 to 20 carbon atoms. According to claim 1,
Component (B-1) is 1,4-butanedioldi(meth)acrylate, 1,6-hexanedioldi(meth)acrylate, 1,9-nonanedioldi(meth)acrylate and neopentylglycol A thermosetting composition of at least one selected from the group consisting of di(meth)acrylates. According to claim 1,
A thermosetting composition in which the component (B) contains a compound having three or more (meth)acryloyl groups. According to claim 1,
A thermosetting composition wherein the components (A) to (C) do not contain a compound having a urethane bond. According to claim 1,
A thermosetting composition comprising 0.1 to 5 parts by weight of component (D) based on 100 parts by weight of the total amount of components (A) to (C). According to claim 1,
A thermosetting composition having a flexural modulus of 2.5 GPa or more in a bending test of a cured product. According to claim 1,
A thermosetting composition in which the cured product has a total light transmittance of 90% or more. A thermosetting composition for producing a resin sheet comprising the composition according to any one of claims 1 to 9. A resin sheet comprising a cured product of the composition according to claim 10. According to claim 11,
A resin sheet whose cured product has a thickness of 100 μm to 5 mm. A method for producing a resin sheet comprising pouring the composition according to claim 10 into a molding mold composed of a base material, a base material for forming a weir, and a base material in this order, followed by heating.

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