JP2022018764A - Curable composition for forming hard coat and laminate - Google Patents

Abstract

To provide a curable composition that can form a hard coat having excellent hardness and chemical resistance as well as high elongation.SOLUTION: The present invention discloses a laminate in which a hard coat, made by curing a hard coat-forming curable composition, is formed on an acrylic resin substrate. Between the resin substrate and the hard coat, a diffusion layer derived from both layers is formed, the diffusion layer having a thickness of 0.3-20 μm.SELECTED DRAWING: Figure 1

Description

The present invention relates to a novel curable composition for forming a hard coat and a laminate.

Acrylic resins such as polymethyl methacrylate (PMMA) are excellent in transparency, impact resistance, processability, etc., and are therefore put into practical use as various molded products. In this case, a hard coat (surface protective layer) is formed on the surface of the molded product in order to increase the hardness (scratch resistance), chemical resistance, etc. of the acrylic resin molded product. As a method of forming a hard coat, there is a method of forming a hard coat by applying a coating liquid for forming a hard coat to a ready-made molded product (post coat method), but in recent years, molding and forming a hard coat have been performed. A method of manufacturing a molded product having a hard coat by insert molding or in-mold molding performed at the same time is also frequently used.

For example, in insert molding, after a sheet-like material for forming a hard coat is loaded into the cavity of a mold, the mold is closed and a heated and melted resin is injected and injected to integrate the sheet-like material and the molten resin. It is a method of producing a plastic molded product. According to this method, in addition to being able to simplify the manufacturing process as compared with the post-coating method, it is possible to form a hard coat even on a molded product having a complicated shape, and the hard coat is firmly integrated into the molded product. There is an advantage that it can be made to.

In this case, when the sheet-like material is to be molded together with the sheet-like material such as insert molding, the sheet-like material is required to have not only hardness and chemical resistance but also formability of the sheet-like material itself. Will be done. Further, in order to obtain high formability, it is also necessary that the elongation (elongation) of the material itself is high.

Techniques for forming such a hard coat include, for example, urethane which is a reaction product of at least (a-1) polyisocyanate, (a-2) polycarbonate polyol, and (a-3) hydroxyalkyl (meth) acrylate. An active energy ray-curable resin composition containing a (meth) acrylate-based oligomer (A), wherein the diol constituent unit of the polycarbonate polyol (a-2) contains 1,4-butanediol and is irradiated with active energy. There is known an active energy ray-curable resin composition characterized by having a tensile elastic coefficient of 100 to 1000 MPa at 23 ° C. of the cured film cured by the above (Patent Document 1).

Further, for example, a polyurethane compound (A) having a weight average molecular weight of 3000 to 50,000 and a side chain radical polymerizable group equivalent of 1000 g / mol or less, and a weight average molecular weight of 5000 to 50,000 and a radical polymerizable group equivalent of 600. A curable composition comprising an acrylic polymer compound (B) having an amount of about 3500 g / mol and a polymerization initiator (C), wherein the polyurethane compound (A) is contained in the following compound: (a1) molecule. A compound having two hydroxyl groups and one radically polymerizable group; (a2) a compound having one hydroxyl group and one or more radically polymerizable groups in a molecule; and (a3) a reaction of a diisocyanate compound. The curable composition, which is a product, has been proposed (Patent Document 2).

Japanese Unexamined Patent Publication No. 2014-196430 Japanese Unexamined Patent Publication No. 2018-172638

When a sheet-like material is subjected to molding processing such as insert molding, formability (processability) capable of forming a desired shape without any trouble is required. However, when a hard coat is formed by using a sheet-like material, hardness, chemical resistance and the like are required.

However, in general, moldability, hardness, and chemical resistance are contradictory to each other, and when the moldability is increased, the hardness or chemical resistance is lowered, while the hardness or chemical resistance is improved. If it is increased, the moldability will decrease. In this respect, even with the curable composition of the prior art, although some formability can be obtained, the hardness, chemical resistance and the like are still not sufficient, and further improvement is required.

Therefore, a main object of the present invention is to provide a curable composition capable of forming a hard coat having high hardness and chemical resistance as well as high elongation.

As a result of diligent research in view of the problems of the prior art, the present inventor has found that the above object can be achieved by adopting a composition having a specific composition, and has completed the present invention.

That is, the present invention relates to the following curable composition for forming a hard coat and a laminate.
1. 1. A curable composition for forming a hard coat on an organic resin substrate.
(1) a) Urethane (meth) acrylate compound having a radical polymerizable group equivalent of 300 g / mol or more and b) (Meta) acrylate compound having a radical polymerizable group equivalent of 300 g / mol or more (however, urethane (meth) acrylate compound) At least one of),
(2) A (meth) acrylate compound having a radically polymerizable group equivalent of 160 g / mol or less, (3) a photopolymerization initiator and (4) an organic solvent, and
The organic solvent is used in Hansen's three-dimensional space according to the following formula (a):
6.5 ≧ {4 (δ _1d －δ _2d ) ² + (δ _1p －δ _2p ) ² + (δ _1h －δ _2h ) ² } ^1/2 ... (a)
(However, δ _1d is the dispersion component of the organic resin base material, δ _2d is the dispersion component of the organic solvent, δ _1p is the polar component of the organic resin base material, δ _2p is the polar component of the organic solvent, and δ _1h is the organic resin base material. The hydrogen-bonded component of δ _2h indicates the hydrogen-bonded component of the organic solvent.)
Meet, meet
A curable composition for forming a hard coat.
2. 2. Item 2. The hard coat formation according to Item 1, wherein the organic resin substrate has a dispersion component δ _1d of 10 to 30, a polar component δ _1p of 0 to 20, and a hydrogen bond component δ _1h of 0 to 20. For curing composition.
3. 3. Item 2. The curable composition for forming a hard coat according to Item 1 or 2, wherein the content of the compound of (2) is 5 to 20% by weight in the solid content.
4. A laminate in which a hard coat formed by curing the hard coat forming curable composition according to any one of Items 1 to 3 is formed on the surface of an organic resin base material, and the same as the organic resin base material. A laminate characterized in that a diffusion layer having a thickness of 0.3 to 20 μm derived from both layers is formed between layers with a hard coat.
5. Item 4. The laminate according to Item 4, which is used for insert molding or in-mold molding.
6. 6. A molded product obtained by molding the laminate according to Item 5. A method for producing a laminate having a hard coat on the surface of an organic resin base material.
(1) A step of forming a liquid film on the surface of an organic resin base material with the curable composition for forming a hard coat according to any one of Items 1 to 3.
(2) A step of forming a hard coat on the organic resin substrate by heat-treating the liquid film or the dry film thereof and then performing a curing treatment.
A method for manufacturing a laminated body, which is characterized by the above.
8. Item 2. The production method according to Item 7, wherein the heat treatment temperature is 70 to 120 ° C.

According to the present invention, it is possible to provide a curable composition capable of forming a hard coat having excellent hardness and chemical resistance as well as high elongation. Therefore, it can be suitably used as a material for forming a hard coat (surface protective layer) of a sheet-like material used for insert molding. The laminate having a hard coat formed by the curable composition of the present invention on the surface can obtain high moldability even when subjected to insert molding or the like, and is integrally molded with the molten resin introduced at the time of molding. It is possible to provide a molded product. At the same time, the hard coat covering the surface of such a molded product can also achieve high hardness, chemical resistance and the like.

The curable composition of the present invention having such characteristics and the hard coat thereof have, for example, an automobile interior material such as a car navigation system and an instrument panel, an automobile exterior material such as a side mirror cover, a mobile phone, a touch panel, a compact disc, and an audio device. , Others, such as electrical equipment, can be suitably used for articles that require high hardness, chemical resistance, etc. on the surface of the product.

It is a figure which shows the layer structure example of the laminated body of this invention. It is an image diagram which shows the HSP distance in three-dimensional space of Hansen.

1. 1. Curable composition for forming a hard coat The curable composition for forming a hard coat of the present invention (the composition of the present invention) is a curable composition for forming a hard coat on an organic resin substrate.
(1) a) Urethane (meth) acrylate compound having a radically polymerizable group equivalent of 300 g / mol or more (hereinafter, also simply referred to as “urethane (meth) acrylate compound”) and b) Radical polymerizable group equivalent of 300 g / mol. At least one of the above (meth) acrylate compounds (excluding urethane (meth) acrylate compounds) (hereinafter, also simply referred to as "(meth) acrylate compound").
(2) A (meth) acrylate compound having a radically polymerizable group equivalent of 160 g / mol or less (hereinafter, also simply referred to as “diffusion component”).
It contains (3) a photopolymerization initiator and (4) an organic solvent, and
The organic solvent is used in Hansen's three-dimensional space according to the following formula (a):
6.5 ≧ {4 (δ _1d －δ _2d ) ² + (δ _1p －δ _2p ) ² + (δ _1h －δ _2h ) ² } ^1/2 ... (a)
(However, δ _1d is the dispersion component of the organic resin base material, δ _2d is the dispersion component of the organic solvent, δ _1p is the polar component of the organic resin base material, δ _2p is the polar component of the organic solvent, and δ _1h is the organic resin base material. The hydrogen-bonded component of δ _2h indicates the hydrogen-bonded component of the organic solvent.)
Meet, meet
It is characterized by that.

In the present invention, unless otherwise specified, acryloyl group or methacryloyl group is collectively referred to as "(meth) acryloyl group". Acryloyloxy group or methacryloyloxy group is collectively referred to as "(meth) acryloyloxy group". Further, acrylate or methacrylic acid is collectively referred to as "(meth) acrylate", and acrylic acid or methacrylic acid is collectively referred to as "(meth) acrylic acid".

Further, the "radical polymerizable group equivalent" in the present invention indicates the molecular weight per mole of the radically polymerizable group. The radically polymerizable group is not limited as long as it is a functional group capable of radical polymerization, and examples thereof include a vinyl group, an allyl group, an acryloyl group, a methacryloyl group, an acryloyloxy group, and a methacryloyloxy group. In particular, at least one of acryloyl group, methacryloyl group, acryloyloxy group and methacryloyloxy group is desirable from the viewpoint of exhibiting high UV curability and the like.

The radically polymerizable group equivalent can be measured by a known measuring method. For example, it can be calculated by the peak ratio of the double-bonded proton to the whole proton by ¹ H-NMR, as well as by iodine value titration or the like.

(1) Urethane (meth) acrylate compound or (meth) acrylate compound In the composition of the present invention, a) a urethane (meth) acrylate compound having a radically polymerizable group equivalent of 300 g / mol or more and b. ) At least one of (meth) acrylate compounds (excluding urethane (meth) acrylate compounds) having a radically polymerizable group equivalent of 300 g / mol or more is used.

As these compounds, those having a radically polymerizable group equivalent of 300 g / mol or more (preferably 350 g / mol or more) are used. This makes it possible to form a hard coat having high elongation, high hardness, high chemical resistance, and the like. The upper limit of the radically polymerizable group equivalent is not particularly limited, but may be, for example, about 10,000 g / mol.

In the present invention, as the urethane (meth) acrylate compound or the (meth) acrylate compound, a compound having a radically polymerizable group equivalent of 300 g / mol or more and having an ultraviolet curable property can be preferably used. For example, those shown in the following (1-1) and (1-2) can be used.

(1-1) Urethane (meth) acrylate compound The urethane (meth) acrylate compound is a compound having a (meth) acryloyl group and a urethane bonding portion, and known or commercially available compounds can be used. Further, those synthesized by a known manufacturing method can also be used. For example, a compound obtained by reacting a (meth) acrylate compound containing a hydroxyl group with a polyvalent isocyanate compound and, in some cases, a polyol compound can be preferably used. Hereinafter, each compound used as a raw material will be described.

(Meta) acrylate compound containing a hydroxyl group Examples of the (meth) acrylate compound containing a hydroxyl group include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, and 4-. Hydroxyalkyl (meth) acrylates of alkyl groups such as hydroxybutyl (meth) acrylates and 6-hydroxyhexyl (meth) acrylates having 1 to 16 (preferably 1 to 12) carbon atoms; 2-hydroxyethyl (meth) acryloyl phosphate. , 2- (meth) acryloyloxyethyl-2-hydroxypropylphthalate, caprolactone-modified 2-hydroxyethyl (meth) acrylate, dipropylene glycol (meth) acrylate, fatty acid-modified-glycidyl (meth) acrylate, polyethylene glycol mono (meth) ) Acrylate, a compound having one ethylenically unsaturated group such as polypropylene glycol mono (meth) acrylate, ethylene such as glycerindi (meth) acrylate and 2-hydroxy-3- (meth) acryloyl-oxypropyl (meth) acrylate. Compound having two sex unsaturated groups, pentaerythritol tri (meth) acrylate, caprolactone-modified pentaerythritol tri (meth) acrylate, ethylene oxide-modified pentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, caprolactone-modified Examples thereof include compounds having three or more ethylenically unsaturated groups such as dipentaerythritol penta (meth) acrylate, ethylene oxide-modified dipentaerythritol penta (meth) acrylate, and succinic acid-modified pentaerythritol tri (meth) acrylate.

Polyvalent isocyanate compound Examples of the polyhydric isocyanate compound include aromatic polys such as tolylene diisocyanate, diphenylmethane diisocyanate, polyphenylmethane polyisocyanate, modified diphenylmethane diisocyanate, xylylene diisocyanate, tetramethylxylylene diisocyanate, phenylenedi isocyanate, and naphthalene diisocyanate. Isocyanate; aliphatic polyisocyanates such as hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, lysine diisocyanate, lysine triisocyanate; hydrogenated diphenylmethane diisocyanate, hydrogenated xylylene diisocyanate, isophorone diisocyanate, norbornene diisocyanate, 1,3-bis ( In addition to alicyclic polyisocyanates such as isocyanatomethyl) cyclohexane, examples thereof include isocyanate trimers or multimers (adducts, bullets, isocyanurates, allophanates). These may be used individually by 1 type, or may be used in combination of 2 or more type.

Polyol compounds Examples of the polyol compound include an aliphatic polyol (A), an alicyclic polyol (B), a polyether polyol (C), a polyester-based polyol (D), a polycarbonate-based polyol (E), and a polyolefin-based polyol (F). ), Polybutadiene-based polyol (G), (meth) acrylic-based polyol (H), polysiloxane-based polyol (I) and the like.

Examples of the aliphatic polyol (A) include ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, trimethylene glycol, dimethylol propane, neopentyl glycol, 2,2-diethyl-1,3-propanediol and 2-butyl. -2-Ethyl-1,3-propanediol, 1,4-tetramethylenediol, 1,3-tetramethylenediol, 2-methyl-1,3-trimethylenediol, 1,5-pentamethylenediol, 1, 6-hexamethylenediol, 3-methyl-1,5-pentamethylenediol, 2,4-diethyl-1,5-pentamethylenediol, pentaerythritol di (meth) acrylate, 1,9-nonanediol, 2-methyl Fatal alcohols containing two hydroxyl groups such as -1,8-octanediol, polyalcohols such as xylitol and sorbitol, and fats containing three or more hydroxyl groups such as glycerin, trimethylolpropane and trimethylolethane. Examples include group alcohols. These can be used alone or in combination of two or more.

Examples of the alicyclic polyol (B) include cyclohexanediols such as 1,4-cyclohexanediol and cyclohexyldimethanol, hydrogenated bisphenols such as hydrogenated bisphenol A, and tricyclodecanedimethanol. One type or two or more types can be used in combination.

Examples of the polyether-based polyol (C) include alkylene structure-containing polyether-based polyols such as polyethylene glycol, polypropylene glycol, polytetramethylene glycol, polybutylene glycol, polypentamethylene glycol, and polyhexamethylene glycol, as well as these polyalkylenes. Random or block copolymers of glycol can be mentioned.

The polyester-based polyol (D) includes, for example, a condensation polymer of a polyhydric alcohol and a polyvalent carboxylic acid; a ring-opening polymer of a cyclic ester (lactone); a polyhydric alcohol, a polyvalent carboxylic acid, and a cyclic ester. Examples thereof include reactants depending on the components.

Examples of the polyhydric alcohol include ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, trimethylene glycol, 1,4-tetramethylenediol, 1,3-tetramethylenediol, and 2-methyl-1,3-trimethylethylenediol. , 1,5-pentamethylene diol, neopentyl glycol, 1,6-hexamethylene diol, 3-methyl-1,5-pentamethylene diol, 2,4-diethyl-1,5-pentamethylene diol, glycerin, tri Examples thereof include methylolpropane, trimethylolethane, cyclohexanediols (1,4-cyclohexanediol and the like), bisphenols (bisphenol A and the like), sugar alcohols (xylitol, sorbitol and the like) and the like.

Examples of the polyvalent carboxylic acid include aliphatic dicarboxylic acids such as malonic acid, maleic acid, fumaric acid, succinic acid, glutaric acid, adipic acid, suberic acid, azelaic acid, sebacic acid and dodecandionic acid; 1,4-cyclohexane. Alicyclic dicarboxylic acids such as dicarboxylic acids; aromatic dicarboxylic acids such as terephthalic acid, isophthalic acid, orthophthalic acid, 2,6-naphthalenedicarboxylic acid, paraphenylenedicarboxylic acid, and trimellitic acid can be mentioned.

Examples of the cyclic ester include propiolactone, β-methyl-δ-valerolactone, ε-caprolactone and the like.

Examples of the polycarbonate-based polyol (E) include a reaction product of a polyhydric alcohol and phosgene; a ring-opening polymer of a cyclic carbonate ester (alkylene carbonate or the like).
The polycarbonate polyol may be a compound having a carbonate bond in the molecule and having a hydroxyl group at the end, and may have an ester bond together with the carbonate bond.

Examples of the polyolefin-based polyol (F) include those having a homopolymer or copolymer of ethylene, propylene, butene or the like as a saturated hydrocarbon skeleton and having a hydroxyl group at the molecular terminal thereof.

Examples of the polybutadiene-based polyol (G) include those having a copolymer of butadiene as a hydrocarbon skeleton and having a hydroxyl group at the molecular terminal thereof.

The polybutadiene-based polyol may be a hydrogenated polybutadiene polyol in which all or part of the ethylenically unsaturated group contained in the structure is hydrogenated.

Examples of the (meth) acrylic polyol (H) include those having a (meth) acrylic acid ester having at least two hydroxyl groups in the molecule of the polymer or copolymer, and such (meth) acrylic acid. Examples of the ester include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, hexyl (meth) acrylate, octyl (meth) acrylate, and (meth). ) 2-Ethylhexyl acrylate, decyl (meth) acrylate, dodecyl (meth) acrylate, octadecyl (meth) acrylate and the like (meth) acrylic acid alkyl esters and the like can be mentioned.

Examples of the polysiloxane-based polyol (I) include dimethylpolysiloxane polyol and methylphenylpolysiloxane polyol.

Among these polyol compounds, an aliphatic polyol or an alicyclic polyol is preferably used in order to suppress stickiness when the resin composition is cured to form a coating film. On the other hand, from the viewpoint of imparting the flexibility of the coating film, polyester-based polyols, polyether-based polyols or polycarbonate-based polyols are preferably used. Further, as the polyol compound, it is preferable to use a bifunctional polyol (having two hydroxyl groups), and a trifunctional polyol may be used in combination.

As described above, a particularly preferred embodiment is obtained by reacting a (meth) acrylate compound containing a hydroxyl group, a polyhydric isocyanate compound, and optionally a polyol compound at an appropriate temperature in the presence of an appropriate catalyst. The urethane (meth) acrylate compound used in the above can be obtained. The urethane (meth) acrylate compound used in the embodiment can also be obtained by reacting the polyol compound with the (meth) acrylate compound containing an isocyanate group at an appropriate temperature in the presence of an appropriate catalyst.

As such a urethane (meth) acrylate compound, a commercially available product can also be used. For example, the purple light series manufactured by Nippon Synthetic Chemistry Co., Ltd. ("UV-7000B", "UV-6640B", etc.), the Eveclil series manufactured by Daicel Ornex Co., Ltd. ("EBECRYL9260", etc.), and Unidic manufactured by DIC Corporation. A series and the like are exemplified. These may be used alone or in admixture of two or more. If necessary, these urethane (meth) acrylate compounds can be appropriately selected or combined to obtain a laminate having desired hardness and elongation.

(1-2) (Meta) Acrylate Compound The (meth) acrylate compound may be a compound other than the urethane (meth) acrylate compound and having at least an acryloyl group, a methacryloyl group, an acryloyloxy group, and a methacryloyloxy group. It should be good, and is not particularly limited. These can be used in one kind or two or more kinds.

In particular, in the present invention, a compound (polymer) having a (meth) acryloyl group at least on the side chain or the terminal of the acrylic main chain can be preferably used.

As the acrylic main chain, a structure composed of a polymer or a copolymer containing (meth) acrylic acid or an ester thereof as a monomer can be adopted. Examples of the (meth) acrylic acid ester include methyl (meth) acrylic acid, ethyl (meth) acrylic acid, propyl (meth) acrylic acid, butyl (meth) acrylate, hexyl (meth) acrylic acid, and (meth) acrylic acid. In addition to (meth) acrylic acid alkyl esters such as octyl, 2-ethylhexyl (meth) acrylate, decyl (meth) acrylate, dodecyl (meth) acrylate, and octadecyl (meth) acrylate, epoxy (meth) acrylate and the like. Can be mentioned.

As such a (meth) acrylate compound, a commercially available product can also be used. For example, UV curable acrylic polymer manufactured by Kyoeisha Chemical Co., Ltd. ("SMP-360A", "SMP-550A"), ART CURE series manufactured by Negami Kogyo Co., Ltd. ("OAP-2531", "OAP-5000", "MAP-" 2801 ”,“ MAP-4050 ”,“ MAP-7000 ”), epoxy acrylate manufactured by Daicel Ornex Co., Ltd. (“EBECRYL3701”, “EBECRYL3708”) and the like can be mentioned. In addition to these, commercially available (meth) acrylate compounds as ultraviolet curable compounds can also be used.

The content (solid content ratio) of the compound (1) in the composition of the present invention is not limited, and may be usually about 50 to 95% by weight, but particularly 70 to 90% by weight. Is preferable. By setting within this numerical range, it is possible to secure higher elongation, better hardness, chemical resistance and the like.

(2) (Meta) acrylate compound as a diffusion component As the (meth) acrylate compound as a diffusion component, a compound having a radically polymerizable group equivalent of 160 g / mol or less (preferably 100 g / mol or less) is used. This makes it possible to form a desired diffusion layer. In this case, the lower limit of the radically polymerizable group equivalent is not particularly limited, but may be, for example, about 80 g / mol.

Further, in the present invention, the weight average molecular weight (hereinafter, simply referred to as “molecular weight”) of the (meth) acrylate compound as a diffusion component is not limited, but is usually preferably 600 or less, and among them, 550. The following is more preferable. Thereby, the diffusion layer can be formed more reliably. The lower limit of the molecular weight is not particularly limited and may be, for example, about 100.

As the (meth) acrylate compound as a diffusion component, for example, a compound having an ethylenically unsaturated group in the molecule such as a vinyl group, an allyl group, an acryloyl group, a methacryloyl group, an acryloyloxy group, and a methacryloyloxy group can be used. However, the urethane (meth) acrylate compound is excluded. Here, the (meth) acrylate compound may be either monofunctional or polyfunctional. Moreover, these can also be used together.

The (meth) acrylate compound as a diffusion component is not limited as long as it has at least the above-mentioned radically polymerizable group equivalent. For example, pentaerythritol triacrylate (radical polymerizable group equivalent 99 g / mol, molecular weight 298), pentaerythritol tetraacrylate (radical polymerizable group equivalent 88 g / mol, molecular weight 352), 1,6-hexanediol diacrylate (radical polymerizable). Base equivalent 113 g / mol, molecular weight 226), ethoxylated isocyanuric acid triacrylate (radical polymerizable group equivalent 141 g / mol, molecular weight 423), trimethylolpropane triacrylate (radical polymerizable group equivalent 98 g / mol, molecular weight 296), di Pentaerythritol hexaacrylate (radical polymerizable group equivalent 96 g / mol, molecular weight 578), 2-hydroxyethyl methacrylate (radical polymerizable group equivalent 130 g / mol, molecular weight 130), acryloylmorpholin (radical polymerizable group equivalent 141 g / mol, One kind or two or more kinds such as molecular weight 141) can be used.

The content (solid content ratio) of the diffusion component in the composition of the present invention may be usually about 5 to 20% by weight, but is particularly preferably 10 to 20% by weight. By setting within this numerical range, more excellent hardness, chemical resistance and the like can be ensured, and high elongation can be obtained more reliably by promoting the formation of the diffusion layer.

(3) Photopolymerization Initiator As a photopolymerization initiator, for example, a) a photo-radical polymerization initiator that generates a radically active species by irradiation with light (for example, acetylbenzene, dimethoxybenzyl, dibenzoyl, benzoin, benzophenone, benzoylbenzoic acid, bis). (Dimethylamino) benzophenone, bis (diethylamino) benzophenone, chlorothioxaton, ethylanthraquinone, etc.), b) Photocationic polymerization initiator that produces a cationically active species (eg, bis (4-tert-butylphenyl) iodonium hexafluorophos. Fert, bis (4-fluorophenyl) iodonium trifurate, diphenyl iodonium hexafluorophosphart, 2,4-bis (trichloromethyl) -6- [2- (fran-2-yl) vinyl] -1,3,5- Triazine, 4-nitrobenzenediazonium tetrafluoroborate, etc.), c) Photoanionic polymerization initiator that generates anionic active species (acetophenone-O-benzoyloxime, cyclohexylcarbamic acid 1,2-bis (4-methoxyphenyl)- 2-oxoethyl, nifedipine, etc.) can be used. These may be used alone or in admixture of two or more.

As such a photopolymerization initiator, a commercially available product can also be used. For example, a commercially available product such as the Irgacure series (BASF Japan) can be used. More specifically, "Irgacure 907" (2-methyl-1- (4- (methylthio) phenyl) -2-morpholinopropane-1-one), "Irgacure TPO" (2,4,6-trimethylbenzoyl-). Diphenyl-phosphine oxide) and the like can be used.

The content (solid content ratio) of the photopolymerization initiator in the composition of the present invention can be appropriately set depending on the type of the polymerization initiator used and the like, but is usually about 2 to 8% by weight. In particular, it is preferably 3 to 5% by weight. By setting within this numerical range, a coating film having excellent hardness, chemical resistance and elongation can be obtained.

(4) Organic solvent The organic solvent is used in Hansen's three-dimensional space according to the following formula (a):
6.5 ≧ {4 (δ _1d －δ _2d ) ² + (δ _1p －δ _2p ) ² + (δ _1h －δ _2h ) ² } ^1/2 ... (a)
(However, δ _1d is the dispersion component of the organic resin base material, δ _2d is the dispersion component of the organic solvent, δ _1p is the polar component of the organic resin base material, δ _2p is the polar component of the organic solvent, and δ _1h is the organic resin base material. The hydrogen-bonded component of δ _2h indicates the hydrogen-bonded component of the organic solvent.)
Use the one that satisfies. By using such an organic solvent, the desired diffusion layer can be more reliably formed in combination with the action of the diffusion component.

Organic by plotting the dispersion component (δ _d ), polar component (δ _p ) and hydrogen bond component (δ _h ) of the organic resin base material and the organic solvent in Hansen's three-dimensional space as shown in FIG. The vector A of the resin base material and the vector B of the organic solvent can be shown. The lengths _LA and LB of each of these vectors are the solubility parameters of _Hildebrand in the organic resin base material and the organic solvent. The above formula (a) is a distance D (hereinafter, also referred to as “HSP distance”) between the tips (arrow portions) of both vectors A and B, and the shorter the distance D, the higher the solubility in general. In the present invention, by controlling such HSP distance to 6.5 or less (preferably 6 or less), a predetermined diffusion layer can be effectively formed in the laminated body.

The lower limit of the HSP distance is not particularly limited and can be usually 0, but for example, when high transparency is required for the laminated body, it is preferably about 0.5, and particularly about 1. It is more preferable to do.

Generally, the organic resin base material on the market has a dispersion component of about 10 to 30, a polar component of about 0 to 20, and a hydrogen bond component of about 0 to 27, so that the organic resin base material to be used (at least forms a diffusion layer) is formed. An organic solvent having an HSP distance of 6.5 or less can be appropriately selected depending on the resin constituting the surface to be formed. Therefore, in the present invention, for example, the dispersion component is 10 to 30 (preferably 15 to 30), the polar component is 0 to 20 (preferably 3 to 17), and the hydrogen bond component is 0 to 20 (preferably 1). The organic resin base material according to to 18) can also be preferably used.

The dispersion component (δ _d ), the polar component (δ _p ), and the hydrogen bond component (δ _h ) of the organic solvent and the organic resin base material in the present invention may be either literature values or actually measured values, but both of them may be used. If it is significantly different, it is desirable to use the measured value. The measured value can be carried out according to a known method. For example, either a method of extracting data from a database of commercially available HSP calculation software, a method of obtaining a molten sphere from a solubility test of an organic resin substrate, and a method of obtaining the center coordinates can be adopted. If an error occurs in each numerical value, the smallest value may be adopted.

The organic solvent that can be used is not limited as long as the above conditions are satisfied, and for example, an ester solvent such as ethyl acetate, butyl acetate, methoxybutyl acetate, methoxypropyl acetate; acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, etc. Ketone solvent; ether solvent such as diethyl ether, dibutyl ether, tetrahydrofuran, propylene glycol monomethyl ether acetate, diethylene glycol dimethyl ether, aromatic solvent such as toluene and xylene, methanol, ethanol, 1-propanol, isopropyl alcohol, ethylene glycol monomethyl One or two or more kinds can be appropriately selected and used from various organic solvents such as alcohol solvents such as ether and propylene glycol monomethiel ether.

The dispersion component, the polar component, and the hydrogen bond component when two or more kinds of organic solvents were mixed were obtained by multiplying each of the dispersion component, the polar component, and the hydrogen bond component of each organic solvent by the volume fraction. The total value is taken as the dispersion component, the polar component and the hydrogen bond component of the mixed solvent.

When an organic solvent is used, the amount used is not limited, and for example, the type of components used, the desired viscosity, etc., so that the solid content of the composition of the present invention is in the range of about 5 to 90% by weight, etc. It may be set appropriately according to the above. For example, when the composition of the present invention is used as a paste, the solid content may be set to be large.

(5) Form of the composition of the present invention The form of the composition of the present invention is usually liquid. The viscosity (20 ° C.) in this case can be appropriately set according to the desired thickness of the hard coat and the like, and can be set to, for example, about 1 to 500 mPa · s, but is not limited thereto.

(6) Production of the Composition of the Present Invention The composition of the present invention can be prepared by uniformly mixing each component as described above. The mixing order and the like at the time of mixing are not particularly limited, and any order can be adopted. Mixing can be carried out using a known or commercially available device such as a mixer or a kneader. The atmosphere to be mixed is not particularly limited, and usually, each component may be mixed under normal temperature and pressure.

In the composition of the present invention, a part or all of the components constituting the composition of the present invention may be dissolved in an organic solvent, or may be dispersed without being dissolved. In particular, in the present invention, it is desirable that at least the organic component is a solution dissolved in an organic solvent.

(7) Use of the composition of the present invention By curing the coating film of the composition of the present invention, a hard coat made of a desired cured film can be formed. In particular, an organic resin base material is used as a base material, and the composition of the present invention is applied to the base material and cured to produce a laminate containing a diffusion layer. The details will be described in the following "2. Laminated body and its manufacturing method".

2. 2. Laminated body and method for producing the same (A) Laminated body In the present invention, a hard coat formed by curing the curable composition for forming a hard coat according to any one of claims 1 to 3 is formed on the surface of an organic resin base material. The laminate is characterized in that a diffusion layer having a thickness of 0.3 to 20 μm derived from both layers is formed between the layers of the organic resin base material and the hard coat (the present invention). Laminated body).

An example of the layer structure of the laminated body of the present invention is shown in FIG. In the laminate 10 of the present invention, the hard coat 12 is formed on the surface (upper side) of the organic resin base material 11. That is, the hard coat 12 is formed so as to be exposed on the outermost surface of the laminated body. Then, as an intermediate layer between the two, a diffusion layer 13 derived from both layers is formed. Here, "derived from both layers" means that the components contained in the organic resin base material 11 and the components contained in the hard coat 12 are mixed by diffusing. For example, a layer formed by diffusion generated at the interface between the organic resin base material 11 and the composition of the present invention directly applied onto the base material can be exemplified.

The organic resin base material is not particularly limited, and is, for example, an acrylic resin (polymethylmethacrylate, etc.), an olefin resin (polyethylene, polypropylene, etc.), a polyester resin (polyethylene terephthalate, polybutylene terephthalate, etc.), and a polyamide resin (polybutylene terephthalate, etc.). Nylon, etc.), Polycarbonate resin, Polyurethane resin, Vinyl resin (vinyl chloride resin, Vinyl acetate resin, etc.), Fluorine resin, Silicone resin, etc. be able to. In particular, when transparency is required for the laminate of the present invention, it is preferable to use a transparent organic resin base material. The degree of transparency can be appropriately set according to the use of the laminated body and the like.

In the present invention, for example, an acrylic resin base material can be preferably used. The acrylic resin is not limited as long as it is a polymer containing at least one (meth) acrylic acid and a derivative thereof as a monomer unit. Examples of the derivative include esters, alkali salts, nitriles, amides and the like. Examples of the ester include esters in which the R of COOR of (meth) acrylic acid is a methyl group, an ethyl group, a butyl group, a glycidyl group, a hydroxyethyl group, a hydroxypropyl group, an ethylhexyl group and the like. Examples of the alkaline salt include a potassium salt and a sodium salt of (meth) acrylic acid. Examples of the nitrile include acrylonitrile and methacryllonitrile. Examples of the amide include (meth) acrylic acid amide. Specific examples of the acrylic resin composed of these monomers include polymethyl methacrylate (PMMA) and the like.

Further, the acrylic resin contains an acrylic resin as a main component (usually, the content in the acrylic resin base material is 50% by weight or more, particularly 80% by weight or more) as a resin component as long as the effect of the present invention is not impaired. Anything may be used, and as long as it is used, it may be a mixed resin with other resin components, a polymer alloy, or the like. The other resin components are not particularly limited, and examples thereof include various resin components such as polyolefin (polyethylene, polypropylene, etc.), polyurethane, polyester, polyamide, polystyrene, silicone resin, polyvinyl alcohol, fluororesin, polyvinyl chloride, and the like. .. Examples of such a resin include acrylonitrile / butadiene / styrene resin (ABS resin) and acrylonitrile / styrene resin (AS resin).

Further, the organic resin base material may contain other additives as long as the effects of the present invention are not impaired. Additives include, for example, plasticizers, fillers, colorants (dye, pigment), preservatives, matting agents, antistatic agents, flame retardants, UV absorbers, light stabilizers, antifouling agents, antiblocking agents, antibacterial agents. Examples include agents and antioxidants.

The organic resin base material may be transparent, translucent or opaque. For example, when it is transparent or translucent, the print layer can be visually recognized by laminating the print layer on the base.

The shape of the organic resin base material is not limited, but it is generally desirable to have a sheet shape (plate shape) from the viewpoint of a shape suitable for molding. In this case, another layer may be contained in the surface opposite to the surface to which the composition of the present invention is applied in the sheet-shaped organic resin base material. The other layer may be, for example, a resin layer, a metal layer, or the like, but from the viewpoint of moldability (for example, moldability in insert molding or in-mold molding), one layer or two or more layers of the thermoplastic resin layer are preferable. Can be adopted for. Examples of the thermoplastic resin include polyolefins (polyethylene, polypropylene, etc.), polyurethanes, polycarbonates, polyesters, polyamides, polystyrenes, silicone resins, fluororesins, polyvinyl alcohol, polyvinyl chloride, and the like. As described above, a laminate in which a specific organic resin layer and other resin layers are laminated can also be used as the organic resin base material.

The thickness of the organic resin base material may be, for example, about 0.05 to 1 mm as long as the desired moldability and the like can be secured, but the thickness is not limited to this. In particular, when the above-mentioned laminate is used as an organic resin base material, the thickness of the acrylic resin layer to which the composition of the present invention is applied is not limited, but it is said that a desired diffusion layer is more reliably formed. From the viewpoint, it is desirable to set it to about 0.1 to 0.5 mm.

The diffusion layer is formed between the layers of the organic resin base material and the hard coat. The diffusion layer is derived from an organic resin substrate and a hard coat, and exists as an intermediate buffer layer between the two layers. The diffusion layer is formed at the interface between the organic resin base material when the composition of the present invention is applied, and is formed as a region containing both the component of the organic resin base material and the component of the composition of the present invention. Will be done. By forming such a diffusion layer, the organic tree base material and the hard coat are integrally formed, and as a result, excellent elongation can be given to the laminated body, and as a result, excellent moldability can be exhibited. This makes it possible to suppress or prevent cracks and the like that may occur during molding.

The thickness of the diffusion layer is usually about 0.3 to 20 μm, preferably 1 to 10 μm. When the thickness is less than 0.3 μm, the cushioning effect is low and the elongation is also low. On the other hand, if the thickness exceeds 20 μm, the coating film performance such as hardness and chemical resistance may deteriorate.

The thickness of the diffusion layer can be measured from the reflectance spectrum of light having a constant wavelength using a commercially available film thickness meter, but it can also be measured by an analysis method such as a scanning electron microscope. Can be measured.

The hardcourt layer is formed by the cured product of the composition of the present invention. As shown in FIG. 1, it is exposed on the outermost surface of the laminated body and functions as a protective layer of the laminated body.

The hardcourt layer may be transparent, translucent or opaque. For example, when the hard coat layer is transparent or translucent, the print layer can be visually recognized by laminating the print layer on the base.

The thickness of the hard coat layer can be appropriately set according to the desired hardness, formability, etc., but is usually 2 to 20 μm, and particularly preferably 2.5 to 10 μm. If it is less than 2 μm, curing failure due to oxygen inhibition may occur, and if it exceeds 20 μm, curing failure in the deep part of the coating film may occur.

(B) Method for producing a laminate The laminate of the present invention can be suitably produced by, for example, the following production method. That is, it is a method of manufacturing a laminate having a hard coat on the surface of an organic resin base material.
(1) A step of forming a liquid film of the composition of the present invention on the surface of an organic resin substrate (coating step).
(2) A step of forming a hard coat on the resin substrate by heat-treating the liquid film or a dry film thereof and then performing a curing treatment (hard coat forming step).
including,
The laminate of the present invention can be produced by a method characterized by the above.

Coating step In the coating step, a liquid film according to the composition of the present invention is formed on the surface of the organic resin base material. Since the organic solvent contained in the composition of the present invention has a property of easily dissolving the organic resin base material, the formation of the diffusion layer can be promoted by swelling the surface of the organic resin base material by forming the liquid film.

The method for forming the liquid film is not particularly limited, and for example, a known coating method such as a doctor blade method, a bar coat method, a dipping method, an air spray method, a roller brush method, and a roller coater method can be appropriately used.

The amount of the liquid film applied may be, for example, an amount such that the desired thickness of the cured film is obtained, and the thickness of the obtained cured film is usually within the range of about 1 to 50 μm (preferably within the range of 3 to 15 μm). It can be set appropriately with.

The liquid film may be set within a range of, for example, about 5 to 30 minutes, as long as it holds a sufficient time for the surface of the organic resin base material to swell, but the liquid film is not limited to this. In this case, the holding temperature may be normal temperature (particularly about 10 to 35 ° C.).

Hardcourt forming step In the hardcoat forming step, the liquid film or the dry film thereof is heat-treated and then cured to form a hardcoat on the resin substrate.

The target of the heat treatment is usually the liquid film of the composition of the present invention, but it may be a dry film that has been naturally dried or dried at a temperature of 50 ° C. or lower. In terms of production efficiency and the like, it is desirable to subject the liquid film to heat treatment.

In the heat treatment, the formation of the diffusion layer can be promoted along with the drying of the liquid film. The heat treatment temperature (oven temperature) can be appropriately set within the range of about 70 to 120 ° C. depending on the boiling point of the organic solvent contained in the composition of the present invention. If the temperature is lower than 70 ° C, insufficient diffusion of the coating film components or insufficient drying of the organic solvent is likely to occur, and if the temperature is higher than 120 ° C, the appearance of the film may be deteriorated due to softening of the organic resin base material. In particular, in the present invention, the heat treatment temperature is preferably set to a temperature lower than the boiling point of the organic solvent contained in the composition of the present invention to be used. Based on the heat treatment temperature, it is preferable to use an organic solvent having a boiling point in the range of 75 to 200 ° C. (preferably 100 to 160 ° C.).

After the heat treatment, the coating film is cured. This makes it possible to fix the diffusion layer formed between the layers of the organic resin base material and the hard coat.

The method for curing the coating film is not particularly limited, but a curing method using radiation (active energy rays) can be particularly preferably adopted. Any radiation may be used as long as it has a sufficient energy level for the photopolymerization initiator to cleave. Examples of the radiation include electromagnetic radiation and particle radiation, and it is particularly preferable to use ultraviolet light, infrared light, visible light, far infrared light and the like.

In the present invention, ultraviolet rays can be preferably used because curing can be carried out relatively easily. Further, when irradiating ultraviolet rays, the light source is not limited, and examples thereof include high pressure mercury lamps, iron-doped metal halide lamps, gallium lamps, low pressure mercury lamps, ultrahigh pressure mercury lamps, ultraviolet lasers, and LEDs. Therefore, it can be cured by using a known or commercially available device equipped with these.

When irradiating ultraviolet rays, for example, it is possible to irradiate ultraviolet rays having an energy of an illuminance of 80 to 1000 mW / cm ² and an integrated light amount of 100 to 5000 mJ / cm ² in a wavelength region of about 100 to 400 nm. Not limited. Ultraviolet irradiation can be carried out using a known or commercially available UV irradiation device.

The temperature condition for irradiating with ultraviolet rays is not particularly limited, but is usually set within the range of 100 ° C. or lower. Therefore, for example, it can be preferably carried out even at around room temperature (about 10 to 40 ° C.).

(C) Use of Laminated Body The laminated body of the present invention can be suitably used as a molding material for molding a molded product having a hard coat (surface protective layer) for protecting the surface of the molded product.

The molding method is not particularly limited, but since the laminate of the present invention is usually a sheet-like material, a method suitable for molding and processing the sheet-like material can be preferably adopted. That is, it is preferable to adopt a method of molding by bringing the sheet-shaped laminated body into close contact with the mold. In particular, it can be suitably used as a sheet-like material to be loaded into a mold in insert molding or in-mold molding. This makes it possible to manufacture a molded product in which the hard coat of the laminate of the present invention is arranged as the outermost surface layer.

Since such a molded product has a hard coat made of the laminate of the present invention on the surface as a surface protective layer, it can exhibit high hardness (scratch resistance), chemical resistance and the like. Further, since the laminate of the present invention has excellent moldability (high elongation), it is possible to effectively suppress the occurrence of defects such as cracks on the surface of the hard coat even after molding, resulting in a good appearance. Can be given.

Examples and comparative examples are shown below, and the features of the present invention will be described more specifically. However, the scope of the present invention is not limited to the examples.

Example 1
A curable composition (coating liquid) was prepared by uniformly mixing each component shown in Table 1. Next, a coating liquid was applied with a bar coat (Barcoater No. 8) on the PMMA surface of a multi-layer film (thickness of about 0.3 mm) made of polycarbonate (PC) / polymethylmethacrylate (PMMA) as an organic resin base material. .. This was placed in an oven and heat-treated at 80 ° C. for 3 minutes to remove the organic solvent to obtain a dry coating film. Then, the coating film was UV-cured by irradiating the coating film with ultraviolet rays (illuminance: 500 mW / cm ² , integrated light amount: 500 mJ / cm ² ). In this way, a laminate having a hard coat formed on the acrylic resin base material was obtained. The unit of the content of each component in Table 1 is "% by weight". The content of the resin in Table 1 represents the content of the active ingredient.

Examples 2 to 3, Example 6 and Comparative Examples 1 to 2, Comparative Example 4
A coating liquid was prepared in the same manner as in Example 1 except that the composition shown in Table 1 was adopted as the coating liquid, and a laminate was further prepared.

Example 4
A coating liquid was prepared in the same manner as in Example 1 except that the heat treatment conditions were set to 90 ° C. for 30 minutes, and a laminate was further prepared.

Example 5
A coating liquid was prepared in the same manner as in Example 1 except that the heat treatment conditions were set to 100 ° C. for 30 minutes, and a laminate was further prepared.

Comparative Example 3
Bar coater No. No. 8 is the bar coater No. A coating liquid was prepared in the same manner as in Example 1 except that the coating solution was replaced with 3, and a laminate was further prepared.

Test Example 1
The following items were investigated for the laminates obtained in each Example and Comparative Example. The results are also shown in Table 1. Table 2 shows the HSP distances of the organic resin base material and the organic solvent together with the numerical values of the dispersion component (D component), the polar component (P component) and the hydrogen bond component (H component) of the organic resin base material and the organic solvent. ..

(1) Coating film thickness and diffusion layer thickness The thickness was measured from the reflectance spectrum of light having a constant wavelength using the film thickness measuring system "F20" (FILMETRIS Co., Ltd.). Here, the "coating film thickness" refers to the thickness of the hard coat 12 in FIG.

(2) Appearance It was visually confirmed that there was no abnormality in the coating film. The case where the surface such as yuzu skin had irregularities or the case where cissing occurred was regarded as "abnormality", and the case where such abnormality was not observed was regarded as "no abnormality".

(3) Elongation A tensile test was conducted at a temperature of 130 ° C., and the elongation rate until cracks were visually observed on the surface of the hard coat was measured. A test piece having a size of 5 mm × 100 mm was cut out from each laminated body, and the test was performed at a distance between chucks of 50 mm and a tensile speed of 600 mm / min.

(4) Pencil hardness The hardness of the hard coat surface (coating film with a coating liquid) was measured in accordance with Japanese Industrial Standards JIS-6500-5-4.

(5) Chemical resistance Apply a commercially available sunscreen cream (product name "Neutrogena" manufactured by Johnson & Johnson, SPF100) to the surface of the hard coat, leave it at a temperature of 80 ° C for 30 minutes, and then dry the sunscreen cream. It was visually confirmed that the surface of the hard coat after wiping with a cloth was transparent to white. Those with no change (the hard coat remains transparent) are marked with "○", those with partial whitening are marked with "△", and those with whitening throughout are marked with "×". did.

The meanings of the abbreviations in Tables 1 and 2 are as follows:
a) UV-7000B: Product name "Shikou UV-7000B" Mitsubishi Chemical Corporation, urethane acrylate (2 to 3 acrylate functional groups), radically polymerizable group equivalent: 1400 g / mol
b) SMP-360AP: Product name "SMP-360AP" Kyoeisha Chemical Co., Ltd., acrylic polymer, radically polymerizable group equivalent: 360 g / mol, solid content 50% (diluted solvent: propylene glycol monomethyl ether)
c) M-306: Product name "Aronix M-306" Toa Synthetic Co., Ltd., pentaerythritol triacrylate (number of acrylate functional groups 3, radically polymerizable group equivalent: 99) and pentaerythritol tetraacrylate (number of acrylate functional groups 4, radical polymerization) Mixture with sex radical equivalent: 88) d) Irgacure 907: Product name "Irgacure 907" BASF Japan Co., Ltd., Photopolymerization initiator e) DMF: N, N Dimethylformamide (boiling point 153.0 ° C.), DuPont Co., Ltd. f) AcOBu : Butyl acetate (boiling point 126.3 ° C.), Gordo g Co., Ltd. MEK: Methyl ethyl ketone (boiling point 79.53 ° C.), Kanto Chemical Co., Ltd. h) PGM: Propropylene glycol monomethyl ether (boiling point 120 ° C.)

As is clear from the results in Table 1, in each example, since the diffusion layer thickness is particularly constant, it can be seen that high hardness and high elongation can be obtained.
On the other hand, in Comparative Example 1, the elongation was insufficient because the thickness of the diffusion layer was insufficient. In Comparative Example 2, since the coating film component did not contain a flexible resin component, the elongation was largely insufficient. In Comparative Example 3, since the coating film layer was less than 2 μm, curing failure occurred, and the pencil hardness and chemical resistance were insufficient. In Comparative Example 4, since the diffusion component was not blended, mutual diffusion at the coating film / substrate interface did not occur, and the desired diffusion layer was not formed, so that the elongation was insufficient.

Claims (8)

A curable composition for forming a hard coat on an organic resin substrate.
(1) a) Urethane (meth) acrylate compound having a radical polymerizable group equivalent of 300 g / mol or more and b) (Meta) acrylate compound having a radical polymerizable group equivalent of 300 g / mol or more (however, urethane (meth) acrylate compound) At least one of),
(2) A (meth) acrylate compound having a radically polymerizable group equivalent of 160 g / mol or less, (3) a photopolymerization initiator and (4) an organic solvent, and
The organic solvent is used in Hansen's three-dimensional space according to the following formula (a):
6.5 ≧ {4 (δ _1d －δ _2d ) ² + (δ _1p －δ _2p ) ² + (δ _1h －δ _2h ) ² } ^1/2 ... (a)
(However, δ _1d is the dispersion component of the organic resin base material, δ _2d is the dispersion component of the organic solvent, δ _1p is the polar component of the organic resin base material, δ _2p is the polar component of the organic solvent, and δ _1h is the organic resin base material. The hydrogen-bonded component of δ _2h indicates the hydrogen-bonded component of the organic solvent.)
Meet, meet
A curable composition for forming a hard coat. The hard coat formation according to claim 1, wherein the organic resin base material has a dispersion component δ _1d of 10 to 30, a polar component δ _1p of 0 to 20, and a hydrogen bond component δ _1h of 0 to 20. For curing composition. The curable composition for forming a hard coat according to claim 1 or 2, wherein the content of the compound of (2) is 5 to 20% by weight in the solid content. A laminate in which a hard coat formed by curing the hard coat forming curable composition according to any one of claims 1 to 3 is formed on the surface of an organic resin base material, and the same as the organic resin base material. A laminate characterized in that a diffusion layer having a thickness of 0.3 to 20 μm derived from both layers is formed between layers with a hard coat. The laminate according to claim 4, which is used for insert molding or in-mold molding. A molded product obtained by molding the laminate according to claim 5. A method for producing a laminate having a hard coat on the surface of an organic resin base material.
(1) A step of forming a liquid film on the surface of an organic resin base material with the curable composition for forming a hard coat according to any one of claims 1 to 3.
(2) A step of forming a hard coat on the organic resin substrate by heat-treating the liquid film or the dry film thereof and then performing a curing treatment.
A method for manufacturing a laminated body, which is characterized by the above. The production method according to claim 7, wherein the heat treatment temperature is 70 to 120 ° C.

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