TWI778131B - Siloxane-based curable resin composition, method for forming hard coat film, cured film, laminate, and method for producing laminate - Google Patents

Abstract

The present invention provides a curable resin composition that can achieve atmospheric hardening in a short time and can be effectively used as a hard coating material excellent in scratch resistance, transparency, and the like. A siloxane-based curable resin composition, characterized in that it comprises a partially hydrolyzed condensate of the following (A) components and (B) components and is a partially hydrolyzed condensate with an epoxy equivalent (g/eq) of 200 to 4000 : (A) component, an alkoxysilane having an isocyanurate ring structure or a partial hydrolysis condensate thereof; (B) component, an alkoxysilane having an epoxy group or an oxetanyl group or a part thereof Hydrolysis condensate.

Description

Formation of siloxane-based curable resin composition and hard coat film Method, cured film, laminate, and method for producing laminate

The present invention relates to a siloxane-based curable resin composition useful as a hard coating material excellent in scratch resistance, transparency, low curling properties, and the like. This composition can be applied to various hard coating materials such as electronic parts such as displays and housings, interior decorations of automobiles, home appliance parts, and building parts, for example.

In recent years, from the viewpoint of weight reduction and designability, a member which protects the surface of a resin substrate with a hard coating material having high scratch resistance as a substitute for metal or glass has been used. For a hard coating material, a hard coating liquid is usually applied to a resin substrate to be protected, and as such a hard coating liquid, an acrylic composition is often used.

Acrylic compositions are usually formed by radical reactions irradiated with active energy rays such as ultraviolet rays or electron beams, so they can be hardened in a short time and at low temperatures, and their toughness can be maintained by the composition of the prepared resin, so they are widely used in In coatings, adhesives, etc. However, when curing by radical polymerization reaction is performed in the air, sufficient scratch resistance cannot be ensured by simply increasing the amount of the radical polymerization initiator due to the influence of oxygen inhibition. Therefore, equipment in an inert gas atmosphere such as nitrogen is required, and such a special equipment also raises a problem that the process cost increases.

On the other hand, as a hardening method that can achieve normal atmospheric hardening, gold is added to an epoxy resin or a siloxane-based composition having a hydrolyzable silyl group. It is a method of curing by heating or room temperature, which belongs to an amide compound or a curing agent. However, when curing under low temperature conditions is required depending on the resin base material, there is a problem that a long time is required to obtain a sufficient cured state.

On the other hand, as an atmospheric hardening method using light hardening that can be hardened in a short time, a cationic hardening material obtained by using an epoxy resin or an alkoxysilane condensate having an epoxy group alone or in combination thereof is reported (Patent Document 1 to Patent Document 3). In any of them, about the alkoxysilane condensate used, the silsesquioxane using an alicyclic epoxy group with high cation hardening property is reported in many cases. For this reason, as a condensation catalyst, in order to prevent ring-opening of epoxy groups, hydrolytic condensation under an alkaline catalyst is used rather than hydrolytic condensation under an acidic catalyst. Generally speaking, the siloxane condensates synthesized under alkaline catalysts include cage-type, random-type, and ladder-type, and most of them are cage-type rigid structures. Furthermore, the cross-linking of alicyclic epoxy groups is used. Since the structure is also rigid, the hardness of the obtained film is high, and on the other hand, there is a problem that it is brittle.

[Prior Art Literature]

[Patent Literature]

[Patent Document 1] WO2014/204010

[Patent Document 2] Japanese Patent Laid-Open No. 2015-212353

[Patent Document 3] Japanese Patent Laid-Open No. 2015-053397

The present invention has been made to solve the above-mentioned problems, and an object of the present invention is to provide a silicon that can achieve atmospheric hardening in a short time and is effectively used as a hard coating material excellent in scratch resistance, transparency, low curling, flexibility, and the like Oxane-based curable resin composition and its hard coating.

The inventors of the present invention have repeatedly studied to achieve the above-mentioned object, and as a result, they have found that the above-mentioned problems can be solved by a siloxane-based curable resin composition containing a specific alkoxysilane formulation. this invention.

That is, the first aspect of the present invention is a siloxane-based curable resin composition characterized by comprising a partially hydrolyzed condensate of the following components (A) and (B), wherein the ring of the partially hydrolyzed condensate is Oxygen equivalent (g/eq) is 200~4000: (A) component, the alkoxysilane with isocyanurate ring structure represented by the following general formula (i) or its partial hydrolysis condensate;

(In the formula, R ¹ represents an organic group with 1 to 15 carbon atoms, R ² represents a hydrogen atom or an alkyl group with 1 to 5 carbon atoms, R ³ represents an organic group with 1 to 6 carbon atoms, and a represents a number of 0 to 2. , X independently represents a hydrogen atom, an organic group having 1 to 15 carbon atoms or a silyl alkyl group represented by formula (ii))

(In the formula, R ¹ to R ³ and a have the same meanings as in the above formula (i))

(B) Component, an alkoxysilane having an epoxy group or an oxetanyl group represented by the following formula (iii) or a partial hydrolysis condensate thereof; R ⁴ _b R ⁵ _c Si(OR ⁶ ) _{4- bc} (iii)

(In the formula, R ⁴ and R ⁵ are both directly bonded to Si, R ⁴ represents an organic group with 1 to 15 carbon atoms including an epoxy group or an oxetanyl group, and R ⁵ represents neither epoxy group and an oxetanyl group with 1 to 10 carbon atoms, R ⁶ represents a hydrogen atom or an alkyl group with 1 to 5 carbon atoms, and b and c represent the numbers of 0<b≦1, 0≦c≦2, respectively , b+c represents the number of 0<b+c≦2).

As for the siloxane-based curable resin composition, the ratio of the (A) component to the (B) component is preferably 0.01 mol to 7 mol of the (A) component with respect to 1 mol of the (B) component.

In the first aspect of the present invention, the siloxane-based curable resin is composed of The product is characterized by being a hard coating liquid containing a hardening catalyst as the component (C) and an organic solvent as the component (D).

In a first aspect of the present invention, a method for forming a hard coat film is characterized in that: after the siloxane-based curable resin composition is coated on a base layer or a substrate and dried, then It is hardened by active energy ray irradiation or heating. Furthermore, it can also be heat-processed.

The second aspect of the present invention is a siloxane-based curable resin composition characterized by comprising: a partially hydrolyzed condensate of the (A) component and the (B) component, and a photocationic polymerization of the (C') component Initiator and surface conditioner of component (E), the epoxy equivalent (g/eq) of the partially hydrolyzed condensate is 200 to 4000: (C') component, photocationic polymerization initiator; (E) component , surface conditioners containing fluorine compounds, dimethylsiloxane compounds, or modified forms or derivatives of these.

As for the siloxane-based curable resin composition, the ratio of the (A) component to the (B) component is preferably 0.01 mol to 7 mol of the (A) component with respect to 1 mol of the (B) component.

The component (E) is preferably a surface conditioner having a reactive group that forms a covalent bond with the partially hydrolyzed condensate of the component (A) and the component (B).

In the second aspect of the present invention, the siloxane-based curable resin composition contains an organic solvent as the component (D).

In a second aspect of the present invention, a method for forming a hard coat film is characterized in that: coating the siloxane-based curable resin composition on a base layer or a base layer. After drying, it is hardened by active energy ray irradiation. Furthermore, it is a cured film obtained by curing the siloxane-based curable resin composition.

A third aspect of the present invention is a layered product comprising a hard resin layer and a base material layer, wherein the hard resin layer is composed of a siloxane-based curable resin, a curing catalyst as the component (C), and The hard coating liquid of the organic solvent as the component (D) is formed, and the siloxane-based curable resin contains the partially hydrolyzed condensate of the (A) component and the (B) component, and the epoxy resin of the partially hydrolyzed condensate. The equivalent is 200~4000 (g/eq).

The hard resin layer and the base material of the laminate of the present invention may be laminated with a single layer or a plurality of resin layers interposed therebetween, or a surface treatment layer may be formed on the base material.

Another aspect of the present invention is a method for producing a hard coat film, characterized in that a hard coat solution containing the siloxane-based curable resin composition is applied to a substrate or a resin layer or a surface-treated After drying on the base material, it is hardened by active energy ray irradiation or heating. Thereby, the hard siloxane resin layer containing a hard coat film can be formed on a base material layer via a resin layer as needed, and the laminated body in which the hard coat film was formed on the surface can be obtained.

Another aspect of the present invention is a cured film obtained by curing the siloxane-based curable resin composition.

The siloxane-type curable resin composition of this invention contains the partial hydrolysis-condensation product of the said (A) component and (B) component. The epoxy equivalent of the partially hydrolyzed condensate is 200 to 4000 (g/eq). The siloxane-based curable resin composition of the present invention may be only The partially hydrolyzed condensate may be included, and other components may also be included.

The siloxane-based curable resin composition of the present invention preferably includes a curing catalyst of the component (C) and the photocationic polymerization of the component (C') together with the partially hydrolyzed condensate of the component (A) and the component (B). The initiator, the organic solvent of the component (D), the surface conditioner of the component (E), and further components other than the components (A) to (E) may be included.

(A) component is the alkoxysilane which has the isocyanurate ring structure represented by the said general formula (i), or its partial hydrolysis-condensation product. Since a condensate or hardened|cured material becomes a polybranched structure by (A) component which has an isocyanurate ring structure, it is thought that a bond is extended three-dimensionally long, and brittleness is improved.

In the general formula (i), R ¹ represents an organic group with 1 to 15 carbon atoms, R ² represents a hydrogen atom or an alkyl group with 1 to 5 carbon atoms, R ³ represents an organic group with 1 to 6 carbon atoms, and a represents 0 A number of ~2, X independently represents a hydrogen atom, an organic group having 1 to 15 carbon atoms, or a silylalkyl group represented by the formula (ii). In formula (i) and formula (ii), common symbols have the same meaning.

Among R ¹ , R ² , R ³ and X, when these are organic groups, hydrocarbon groups are preferred, and alkyl groups, alkenyl groups, and cycloalkyl groups are more preferred. Moreover, when carbon number is 6 or more, it may be an aromatic hydrocarbon group.

As X, it is preferable that at least one is a silyl alkyl group represented by the formula (ii), and it is more preferable that both X's are a silyl alkyl group represented by the formula (ii). a is preferably 0 or 1.

Here, the partially hydrolyzed condensate refers to a dimer or more that is a part of an alkoxysilyl group hydrolyzed and partially condensed to have an alkoxysilyl group or a hydroxyl group base condensate. On the other hand, the fully hydrolyzed condensate is distinguished by the fact that the hydroxyl group is substantially consumed by the condensation reaction, so that no further condensation reaction proceeds.

Examples of the alkoxysilane having an isocyanurate ring structure represented by the general formula (i) include 1,3,5-tris(methyldimethoxysilylpropyl)isocyanurate acid ester, 1,3,5-tris(methyldiethoxysilylpropyl)isocyanurate, 1,3,5-tris(trimethoxysilylpropyl)isocyanurate, 1,3,5-Tris(trimethoxysilylethyl)isocyanurate, 1,3-(di-2-propen-1-yl)-5-(3-triethoxysilylpropyl) base) isocyanurate, 1-(2-propen-1-yl)-3,5-bis(3-triethoxysilylpropyl)isocyanurate, 1,3-bis(3 -Trimethoxysilylpropyl)isocyanurate, 1-glycidylmethyl-3,5-bis(3-trimethoxysilylpropyl)isocyanurate, 1,3-bis (Glycidylmethyl)-5-(3-trimethoxysilylpropyl)isocyanurate, 1-glycidylmethyl-3-(2-propen-1-yl)-5-( 3-triethoxysilylpropyl) isocyanurate, 1,3-dimethyl-5-(3-triethoxysilylpropyl) isocyanurate, etc. 1,3,5-tris(trimethoxysilylpropyl)isocyanurate, 1,3,5-tris(methyldiethoxysilylpropyl)isocyanurate, 1,3,5-Tris(trimethoxysilylethyl)isocyanurate.

The component (B) is a siloxane resin which is an alkoxysilane having an epoxy group or an oxetanyl group represented by the formula (iii) or a partial hydrolysis condensate thereof. It is thought that scratch resistance and storage stability are improved by (B) component which has an epoxy group or an oxetanyl group.

In formula (iii), R ⁴ is an organic group having 1 to 15 carbon atoms, preferably 1 to 10 carbon atoms, including an epoxy group or an oxetanyl group. R ⁵ is an organic group having 1 to 10 carbon atoms, preferably an organic group having 1 to 4 carbon atoms, neither containing an epoxy group nor an oxetanyl group. R ⁶ represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, preferably 1 to 2 carbon atoms. The organic group in R ⁴ and R ⁵ is preferably an alkyl group, and the organic group in R ⁴ is preferably an alkyl group having a glycidyl group, an alicyclic epoxy group, or an oxetanyl group at the terminal . In the calculation of the carbon number of the organic group in R ⁴ , the carbon number of an epoxy group or an oxetanyl group is not included. In the case of including the carbon number which an epoxy group or an oxetanyl group has, the carbon number is increased by 2 to 3.

In formula (iii), b and c represent numbers (average values) of 0<b≦1 and 0≦c≦2, respectively, and b+c satisfies 0<b+c≦2. 4-b-c is preferably 2 or number of 3. b is preferably 0.1 or more.

As the alkoxysilane having an epoxy group or an oxetanyl group represented by the formula (iii), for example, 3-glycidyloxypropylmethyldimethoxysilane, 3-glycidyloxy Propyltrimethoxysilane, 4-glycidoxybutyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidyloxy(2-ethyl)propyltrimethoxysilane, 4-glycidylbutyltrimethoxysilane, 8-glycidyloxyoctyltriethoxysilane, 2-(3, 4-Epoxycyclohexyl)ethyltrimethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltriethoxysilane, 3-[(3-ethyloxetane-3- Silane compounds having cyclic ethers, such as propyl)methoxy]propyltrimethoxysilane. Preferred are 3-glycidoxypropyltrimethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-[(3-ethyloxetane-3 -yl)methoxy]propyltrimethoxysilane.

The partially hydrolyzed condensate of the alkoxysilane of the formula (iii) is obtained by partially hydrolyzing it in the same manner as the alkoxysilane of the formula (i).

The compounding ratio (molar ratio) is preferably 0.01 mol to 7 mol of (A) component relative to 1 mol of (B) component, more preferably 0.01 to 1.5 mol.

The partial hydrolysis condensate of (A) component and (B) component is a partial hydrolysis condensate containing the mixture of (A) component and (B) component. In the mixture containing (A) component and (B) component, other silane compound or its (partial) hydrolyzate may be contained unless the objective of this invention is inhibited.

Examples of other silane compounds include methyltrimethoxysilane, dimethyldimethoxysilane, methyltriethoxysilane, dimethyldiethoxysilane, n-propyltrimethoxysilane, n-propyltriethoxysilane, hexyltrimethoxysilane, hexyltriethoxysilane, octyltriethoxysilane, decyltrimethoxysilane, phenyltriethoxysilane, phenyltrimethoxysilane Silane, vinyltriethoxysilane, vinyltrimethoxysilane, p-styryltriethoxysilane, p-styryltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-amine propyltriethoxysilane, 3-chloropropyltriethoxysilane, 3-chloropropyltriethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane , 3-isocyanatopropyltrimethoxysilane, 3-isocyanatopropyltriethoxysilane, 3-methacryloyloxypropyltrimethoxysilane, 3-acryloyloxypropyltrimethoxysilane, Alkoxysilanes such as 3-methacryloyloxypropylmethyldimethoxysilane. These organosilanes may be used alone or in combination of two or more.

The partial hydrolysis condensate of (A) component and (B) component is a partial hydrolysis condensate containing the mixture of (A) component and (B) component. Hydrolysis is preferably carried out to the extent that all alkoxy groups are hydrolyzed to form OH groups, but Si-OH groups are condensed to form silicon The condensation of the oxane bond is partially progressed. If the condensation proceeds too much, gelation proceeds and it cannot be dissolved or dispersed in the solvent. Moreover, after partially hydrolyzing the components (A) and (B) separately, they may be mixed, and further hydrolyzed and condensed may be used.

These hydrolyzed condensates are siloxane resins, and their average molecular weight (Mw) is preferably 300-60,000, more preferably 400-30,000.

The partially hydrolyzed condensate of (A) component and (B) component has an epoxy group or an oxetanyl group, and an epoxy equivalent is 200-4000, Preferably it is 200-1000, More preferably, it is 200-500. From this epoxy equivalent, the molecular weight can also be calculated.

In the present invention, the partially hydrolyzed condensate does not contain catalysts or solvents added during hydrolysis, water remaining unreacted, and water generated during condensation, and refers to compounds containing Si generated during partial hydrolysis and condensation, The so-called siloxane resin component.

Regarding the epoxy equivalent (g/eq), if the epoxy equivalent is less than the lower limit, the scratch resistance and storage stability may decrease. When the epoxy equivalent exceeds the upper limit, the obtained film becomes brittle and the toughness decreases. In the resin composition of the present invention, the term "epoxy equivalent" refers to the mass of the siloxane resin having one equivalent of an epoxy group and does not include a solvent or the like. In addition, even when (B) component has an oxetane group rather than an epoxy group, since an oxetane equivalent becomes the same value as an epoxy equivalent, it can be understood as an epoxy equivalent.

In addition, the epoxy equivalent in a composition can also be adjusted by adding an epoxy resin together with (B) component. As such an epoxy resin, a general-purpose difunctional epoxy resin such as a bisphenol type epoxy resin or a polyfunctional epoxy resin such as a phenol novolak epoxy resin can be used.

Regarding the method of hydrolysis, in order to obtain a chain-like siloxane structure, the solution can be hydrolyzed with acidic water having pH values of 1 to 7, preferably pH 2 to 5. In this pH adjustment, hydrochloric acid, nitric acid, formic acid, acetic acid, propionic acid, oxalic acid, citric acid, maleic acid, benzoic acid, malonic acid, glutaric acid, glycolic acid, methanesulfonic acid, toluene can be used Organic or inorganic acids such as sulfonic acid. Moreover, it can also be used for the cation exchange resin etc. which have a carboxylic acid group or a sulfonic acid group on the surface. The amount of the acid or acid catalyst used is preferably 0.0001% by weight to 20% by weight relative to the product (partially hydrolyzed condensate).

In the hydrolysis reaction, the presence of water is required. The amount of water may be a sufficient amount or more to hydrolyze (a part of) the hydrolyzable groups in the silane compound, and is preferably 0.5 of the theoretical amount (moles) corresponding to the number of hydrolyzable groups Molar to 2.0 times the amount of moles. More preferably, it is 0.7 times mol to 1.5 times mol. In addition, when adding an acid or a catalyst as an aqueous solution, its water is added to a calculation. When there is little water, sufficient hydrolysis cannot be performed, and when there is much water, coatability and drying efficiency are lowered due to the remaining water.

A dehydration condensation reaction of the generated silanol group is generated simultaneously with the hydrolysis, thereby forming a siloxane resin composition. The temperature at which the condensation is performed is normal temperature or under heating at 120°C or lower, more preferably 30°C or higher and 100°C or lower. When the temperature is low, the time for hydrolysis and condensation reaction may become longer and the productivity may be lowered, and when the temperature is higher than the range, there is a fear of becoming insoluble.

Various organic solvents may be mixed for the purpose of adjusting the reaction rates of the hydrolysis and condensation and the molecular weight of the resulting resin composition. For example, examples of alcohols include methanol, ethanol, butanol, isobutanol, isopropanol, propanol, Tributanol, second butanol, benzyl alcohol; as ketones, acetone, methyl ethyl ketone, methyl isobutyl ketone, diisobutyl ketone, cyclohexanone, diacetone alcohol; as esters , ethyl acetate, methyl acetate, butyl acetate, 2-butyl acetate, methoxybutyl acetate, amyl acetate, propyl acetate, isopropyl acetate, ethyl lactate, methyl lactate, lactic acid Butyl ester; ethers include isopropyl ether, methyl cellosolve, ethyl cellosolve, butyl cellosolve; glycols include ethylene glycol, diethylene glycol, triethylene glycol, Propylene glycol; as glycol esters, ethylene glycol monoethyl ether acetate, methoxypropyl acetate, butyl carbitol acetate, ethyl carbitol acetate; as glycol ethers system, including diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, butyl diethylene glycol, methyl triethylene glycol, 1-methoxy-2-propanol, propylene glycol monobutyl ether, 3-methyl glycol Oxy-3-methyl-1-butanol, diethylene glycol monohexyl ether, propylene glycol monomethyl ether propionate, dipropylene glycol methyl ether, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, ethyl Glycol diethyl ether, diethylene glycol diethyl ether; As an aromatic hydrocarbon type, benzene, toluene, and xylene are mentioned. These organic solvents may be used alone or in combination of two or more.

When the whole amount of the component to be hydrolyzed is 100 parts by weight, the mixing amount of the organic solvent is preferably 10 parts by weight to 2000 parts by weight. However, when there are many compounding quantities of (B) component, hydrolysis and condensation can also be performed in the solvent-free state which does not use an organic solvent.

The resin composition in the first aspect of the present invention may be only the partially hydrolyzed condensate, and the partially hydrolyzed condensate has an epoxy group or an oxetanyl group, and is also an epoxy resin, so ( C) A hardening catalyst formulated in the form of a component to harden it.

As the hardening catalyst (C), a hardening agent (acid generator or alkali generator) or a hardening accelerator that generates acid or alkali by heating or active energy ray irradiation can be applied. As a hardening agent which generates an acid or alkali, a diazonium salt, an iodonium salt, a peronium salt, a phosphonium salt, a selenium salt, an oxonium salt, and an ammonium salt can be mentioned.

Specific examples of the thermal acid generator or photoacid generator include San-Aid SI series (manufactured by Sanshin Chemical Co., Ltd.), TA series, or CPI series (San Apro Co., Ltd. manufactured), ADEKA ARKLS SP series (manufactured by ADEKA), WPI series (manufactured by Wako Pure Chemical Industries), etc. Specific examples of the photobase generator include WPBG series (manufactured by Wako Pure Chemical Industries, Ltd.), O0395, A2502 (manufactured by Tokyo Chemical Industry Co., Ltd.), EIPBG (manufactured by EIWEISS), and the like.

In the case of curing by active energy rays, photoinitiator aids or sensitizers such as sensitizers and radical polymerization initiators that are effective in combination may be used in combination. As a hardening accelerator by heating, an amine adduct type, a hydrazine type, and an imidazole type are mentioned. Specifically, AJICURE PN series (manufactured by Ajinomoto Fine Techno), FUJICURE FXR series (manufactured by TOKA), imidazole Compound series (manufactured by Shikoku Chemical Co., Ltd.), etc.

The addition amount of the (C) component is preferably in the range of 0.1 to 10 parts by weight relative to 100 parts by weight of the partially hydrolyzed condensate of the components (A) and (B).

If the range is not satisfied, the crosslinking becomes insufficient, the elastic modulus decreases, and there is no method to obtain the desired surface hardness. Even if it is added beyond this range, further improvement of the reaction rate cannot be expected.

In the resin composition in the second aspect of the present invention, the partially hydrolyzed condensate of the (A) component and the (B) component has an epoxy group or an oxetanyl group, and is also an epoxy resin, so the (C') A photocationic polymerization initiator formulated to be hardened as a component.

The photocationic polymerization initiator (C') is also an acid generator that generates an acid (cation) by active energy ray irradiation. For example, a diazonium salt, an iodonium salt, a pernium salt, a phosphonium salt, an oxonium salt, and an ammonium salt can be mentioned.

Therefore, specifically, the San-Aid SI series (manufactured by Sanshin Chemical Co., Ltd.), TA series or CPI series, IK series (manufactured by San Apro Co., Ltd.), Adiko Akers (ADEKA ARKLS) SP series (manufactured by ADEKA (ADEKA)), WPI series (manufactured by Wako Pure Chemical Industries, Ltd.), Irgacure series (manufactured by BASF (BASF)) and so on.

Among them, when it is a thick film and transparency is required, iodonium salt is preferable. Specifically, IK-1 (manufactured by San Apro Corporation), WPI113, WPI116, WPI170, WPI124 (manufactured by Wako Pure Chemical Industries, Ltd.), Irg250 (manufactured by BASF Corporation), and the like can be exemplified.

Furthermore, photoinitiator aids or sensitizers, such as a sensitizer and a radical polymerization initiator, which are effective in combination with an initiator, may be used in combination.

The addition amount of the component (C') is the same as that of the curing catalyst of the component (C), based on 100 parts by weight of the partially hydrolyzed condensate of the components (A) and (B), It is preferably in the range of 0.1 part by weight to 10 parts by weight, more preferably in the range of 1 part by weight to 7 parts by weight. If it does not satisfy this range, the crosslinking becomes insufficient, the elastic modulus decreases, and the desired surface hardness cannot be obtained. Even if it is added beyond this range, further improvement of the reaction rate cannot be expected. In addition, in a 2nd aspect, when it mixes with the surface conditioner (E) component mentioned later, by setting it as the range of 1 weight part or more, the further improvement of scratch resistance can be aimed at.

The resin composition in the 2nd aspect of this invention contains the surface conditioner of (E) component. The surface conditioner is prepared for the purpose of improving leveling and scratch resistance during film formation. As the surface conditioner, a fluorine compound or a dimethylsiloxane compound, or a modified form or derivative (including oligomer or polymer) of these compounds is used. Specifically, FZ-2123, 57 additive (ADDITIVE) (manufactured by Toray-Dow Corning), KP124, KP109, KP110, KP121, KP106, KP112, KP625 (manufactured by Shin-Etsu Chemical Co., Ltd.) can be exemplified. ), BYK306, BYK307, BYK310, BYK313, BYK333, BYK342 (manufactured by BYK), R40, R41, R43, R94 (manufactured by DIC), Polyflow 401, Polyflow Polyflow 402, Polyflow 404 (manufactured by Kyoeisha Chemical Co., Ltd.), and the like.

Furthermore, as a surface conditioner (E) for maintaining scratch resistance for a long period of time, it is preferable that it has a structure which has a reactive group incorporated in the crosslinking of the partially hydrolyzed condensate of (A) component and (B) component. Examples of the reactive group include a hydroxyl group such as a methanol group and a silanol group, an epoxy group, or a mercapto group, and more preferably a fluorine compound or a dimethylsiloxane compound modified with these reactive groups.

Specifically, KF-1001, KF1002, KF2001, KF-105, KF-6000, KF-6001, KF-6002, KF-6003, X-22-167B, KF9701, X22-173, X-22 can be exemplified -170, X-22-9002 (manufactured by Shin-Etsu Chemical Co., Ltd.), L-7604, 8029 Additive (ADDITIVE), 8054 Additive (ADDITIVE), 8211 Additive (ADDITIVE), 8526 Additive (ADDITIVE) (Toray Dow Corning (Toray-Dow corning), BYK370, BYK375, BYK377, BYKSILCEAN 3700, BYKSILCEAN 3701, BYKSILCEAN 3720 ( BYK (BYK) company) and so on.

With respect to 100 parts by weight of the partially hydrolyzed condensate of the components (A) and (B), the addition amount of the component (E) is preferably 0.01 parts by weight to 5 parts by weight, more preferably 0.05 parts by weight to 2 parts by weight range.

If it does not satisfy this range, the leveling property and scratch resistance at the time of film formation cannot be improved. Even if it is added beyond this range, further improvement cannot be expected, and there is a concern that other physical properties will be hindered.

The siloxane-based curable resin composition of the present invention can be used as a hard coating liquid by including an organic solvent as the component (D). (D) component is an organic solvent. The organic solvent may be the same as the organic solvent mixed at the time of hydrolysis, and may be the same as or different from the solvent mixed at the time of hydrolysis. With respect to 100 parts by weight of the partially hydrolyzed condensate, the compounding amount of component (D) is preferably 10 parts by weight to 5000 parts by weight, more preferably 100 parts by weight to 1000 parts by weight. In addition, the compounding quantity of (D)component is the quantity including the quantity of the solvent mixed at the time of hydrolysis.

It is desirable to form a hard coat film by applying a hard coat liquid containing the above components on a substrate or a primer layer, drying it, and then photocuring it by ultraviolet irradiation. The hardening is caused by the polymerization of epoxy groups or oxetane groups, and also contributes to the addition reaction of epoxy groups or oxetane groups with silanol groups and the condensation of silanol groups. caused by the cross-linking reaction. After photohardening, in order to make the condensation of silanol groups proceed sufficiently, a heat hardening step may be provided.

In the composition of the present invention, other components may be formulated as necessary. Examples of other components include epoxy resins, acrylic resins, organic/inorganic fillers, plasticizers, flame retardants, heat stabilizers, antioxidants, ultraviolet absorbers, ultraviolet shielding agents, lubricants, antistatic agents, deodorizers Molding agents, foaming agents, nucleating agents, colorants, cross-linking agents, dispersing aids, and other resin components for the purpose of promoting the reaction such as other siloxane-based resins, organic acrylates or vinyl compounds, and the like. In the case of preparing acrylic resin or organic acrylate, it is preferable to use a photo-radical polymerization initiator in combination. Modified body.

As a method of forming a hard coat film, a casting method, a roll coating method, a bar coating method, a spray coating method, an air knife coating method, a spin coating method, a flow coating method, a curtain coating method, and a dipping method are mentioned, for example. It should be noted that the coating film thickness is adjusted by the solid content concentration in consideration of the formed film thickness after drying and curing by irradiation with active energy rays.

After the coating of the hard coating liquid, the solvent is preferably removed by drying or the like. The drying temperature is a condition under which the substrate to be used does not deform, and the drying time is preferably 1 hour or less from the viewpoint of productivity.

From the viewpoint of scratch resistance and adhesion, the thickness of the hard coat film is 0.5 μm to 20 μm, preferably 1 μm to 10 μm.

In the hard coat film forming step, when a photoactive curing catalyst is used, the active energy rays are preferably irradiated under the conditions of an illuminance of 100 mW/cm ² or more and a cumulative light amount of 1,000 mJ/cm ² or more. When the irradiation amount is low, the crosslinking formation is insufficient, and the desired performance of scratch resistance cannot be obtained.

After hardening by irradiation with active energy rays, heat treatment may be performed. The hardening temperature is set so that the base material to be used does not deform, and is carried out in order to promote the hydrolysis condensation of the silicone resin, and further, in order to diffuse the generated acid or alkali, the epoxy group or the oxetanyl group is promoted. the hardening reaction. The temperature conditions are 70°C to 150°C, preferably 80°C to 120°C.

The laminated body which is the 3rd aspect of this invention forms the hard siloxane resin layer as a hard coat film on a base material layer via another resin layer as needed.

The hard coat film is formed from a hard coating liquid containing a siloxane-based curable resin, a hardening catalyst (C) and an organic solvent (D), and the siloxane-based curable resin contains the (A) component and ( B) Partially hydrolyzed condensate of component.

As the base material, any of thermoplastic resin, curable resin, metal, glass, wood, paper, and stone can be used. Specifically, as the thermoplastic resin, polyvinyl chloride, polyethylene, polypropylene, polystyrene, acrylonitrile-butadiene-styrene copolymer resin, polymethmethacrylic acid, polyvinyl alcohol, polyvinylidene vinylidene chloride, polyethylene terephthalate, polyamide, polyacetal, polyphenylene ether, polycarbonate, polybutylene terephthalate, polyvinylidene fluoride, polyselenium, polyethersine , polyphenylene sulfide, poly Aryl ester, polyamide imide, polyether imide, polyether ether ketone, polyimide, liquid crystal polymer, polytetrafluoroethylene, cyclic olefin copolymer, elastomer, etc. Examples of curable resins include phenol resins, urea resins, melamine resins, polyester resins, acrylic resins, urethane resins, epoxy resins, imide resins, siloxane resins, and fluororesins. Examples of the metal include steel sheets such as aluminum, magnesium, copper, and iron, alloy steel sheets thereof, and various plated steel sheets. As the wood, zelkova (Zelkova serrata), Japanese cypress (Chamaecyparis obtusa), cedar (Cryptomeria japonica), red pine (Pinus densiflora), African neem (Avodire), rosewood (Rosewood), walnut ( Walnut, teak, Mahogany, white oak, ironwood, cherry, beech, maple, rubber wood, Various woods such as chestnut, hickory, oak, ash (Fraxinus mandshurica), pine (pine), and magnolia (magnolia). Examples of paper include those derived from artificial cellulose fibers; derived from wood such as eucalyptus and acacia; derived from non-wood such as hemp, mulberry, and bamboo, and further include composites with inorganic fine particles, or composites containing resins. etc. Examples of the glass include various types of glass such as float glass, tempered glass, heat-resistant glass, fire-resistant glass, patterned glass, colored glass, laminated glass, and heat ray reflecting glass. Examples of the stone include natural stones such as igneous rocks, sedimentary rocks, and metamorphic rocks, artificial marbles, and the like.

For the purpose of imparting functionality or design properties such as adhesiveness or weather resistance, a single or multi-layer resin layer may also be interposed between the hard resin layer and the substrate. Use a commercially available primer suitable for the substrate or Curable resins such as adhesives and printing materials, when the resin layer is a multilayer, commercially available primer materials suitable for the base resin layer, adhesive materials, and curable resins such as printing materials can be used. As resin, acrylic resin, urethane resin, polyurea resin, epoxy resin, phenol resin, siloxane resin, polyimide resin, polyimide resin, etc. can be illustrated. Specific examples of the resin types of the resin layer include the following resin types, but are not particularly limited.

The acrylic resin is preferably a cured resin obtained by curing an acrylic composition containing a polyfunctional acrylic monomer having a molecular weight of 500 or less. Examples of the polyfunctional acrylic monomer include polyfunctional (meth)acrylates, preferably polyfunctional acrylates having two or three (meth)acrylic groups in the molecule, and examples thereof include aliphatic acrylic acid. ester, alicyclic acrylate, epoxy acrylate, etc. Moreover, in the acrylic composition containing a polyfunctional acrylic monomer, it is preferable to contain the compound which has an epoxy group, and it is more preferable to contain the polyfunctional acrylic monomer containing an epoxy group, such as epoxy acrylate.

Specific examples of the polyfunctional (meth)acrylate include 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, 9-Nanediol di(meth)acrylate, tetraethylene glycol dimethacrylate, dicyclopentyldimethylol di(meth)acrylate, trimethylolpropane tri(meth)acrylic acid ester, pentaerythritol tri(meth)acrylate, polyethylene glycol type epoxy acrylate, trimethylolpropane type epoxy acrylate, urethane acrylic acid obtained by reacting isocyanate and acrylate having a hydroxyl group esters, etc. These (meth)acrylates may be used alone or in combination of two or more.

When curing the acrylic composition, it is preferable to add a photopolymerization initiator as a polymerization initiator, and the amount of the photopolymerization initiator to be added is preferably 0.1 weight part with respect to the total 100 parts by weight of the resin composition. part to 10 parts by weight. If it does not satisfy this range, the crosslinking becomes insufficient, the elastic modulus decreases, and the desired surface hardness cannot be obtained. Conversely, even if it is contained beyond this range, further improvement of the reaction rate cannot be expected.

Examples of the urethane resin include hardened resins of an aliphatic or aromatic polyester polyol compound, a diisocyanate compound, a triisocyanate compound, a polyisocyanate compound, or a melamine resin.

Examples of the polyol include polyester polyols obtained by polycondensation of polybasic acids and polyols; polyester polyols obtained by ring-opening polymerization of lactones such as ε-caprolactone and γ-valerolactone. Alcohols; polyether polyols that are polymers of cyclic ethers such as alkylene oxides such as ethylene oxide, propylene oxide, and butylene oxide, tetrahydrofuran, and alkyl-substituted tetrahydrofuran, or copolymers of two or more of these, etc. .

Examples of the polyisocyanate compound include 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, 4,4'-diphenylmethane diisocyanate, hydrogenated 4,4'-diphenylmethane diisocyanate, diphenylene Tolyl diisocyanate, hydrogenated xylylene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, 1,5-naphthalene diisocyanate, tolidine diisocyanate, p-phenylene diisocyanate, trans Cyclohexane 1,4-diisocyanate, lysine diisocyanate (lysine diisocyanate), tetramethylxylene diisocyanate, lysine ester triisocyanate, 1,6,11-undecanetriisocyanate, 1, 8-Diisocyanate-4-isocyanate methyl octane, 1,3,6-hexamethylene triisocyanate, dicycloheptane triisocyanate, trimethylhexamethylene diisocyanate, dicyclopentadiene diisocyanate, norbornene diisocyanate, etc.

Urethane resin may have reactive groups other than the said reactive group, for example, an amino group, a (meth)acrylate group, a vinyl group, a mercapto group, an epoxy group, etc. are mentioned.

Examples of the polyurea resin include cured resins of polyamines and polyisocyanates. The polyamine has at least two or more amine groups, and may be a primary amine, a secondary amine, or a tertiary amine, and examples thereof include aliphatic amines, aromatic amines, and modified amines. Specifically, 1,2-diaminopropane, 1,5-diamino-2-methylpentane, 1,3-diaminopentane, 1,2-diaminocyclohexyl can be mentioned. Alkane, 1,6-diaminohexane, 1,11-diaminoundecane, 1,12-diaminododecane, 3-(cyclohexylamino)propylamine, 1-amino-3 ,3,5-trimethyl-5-aminomethylcyclohexane, isophoronediamine, 4,4'-diaminodicyclohexylmethane, 3,3'-dimethyl-4, 4'-Diaminodicyclohexylmethane, 3,3'-[1,4-butanediylbis-(oxy)bis]-1-propanamine, menthanediamine, diethylenetriamine, diethylenetriamine Propylene triamine, bis(hexamethylene) triamine, diethylenetetramine, triethylenetetramine, tetraethylenepentamine, diethylenetriamine, triethylenetetramine, dipropylenediamine, diethylaminopropylamine , N-aminoethylpiperazine, menthene diamine, isofluranediamine, m-xylylenediamine, m-phenylenediamine, diaminodiphenylmethane, diaminodiphenylene, etc. As for the polyisocyanate, the same ones described in the above-mentioned urethane resin can be mentioned.

Examples of the epoxy resin include curable resins obtained by curing epoxy resins having at least two or more epoxy groups with isocyanate or melamine resin, and aliphatic epoxy, aromatic epoxy, and modified epoxy can be used. and other well-known epoxy-containing resins. Specifically, bisphenol-type epoxy resin, novolak-type epoxy resin can be mentioned. Aliphatic, aromatic epoxy resin, alicyclic epoxy resin, aliphatic epoxy resin, glycidyl ester type epoxy resin, etc. Examples of bisphenol-type epoxy resins include bisphenol A-type epoxy resins, bisphenol F-type epoxy resins, bisphenol AD-type epoxy resins, bisphenol S-type epoxy resins, and the like, and bromides thereof, water additive. As a novolak-type epoxy resin, a phenol novolak-type epoxy resin, a cresol novolak-type epoxy resin, etc. can be illustrated. Trisphenol methane triglycidyl ether etc. are illustrated as an aromatic epoxy resin. Examples of the modified epoxy resins include epoxy ester resins obtained by reacting a drying oil fatty acid with a part of the epoxy groups of epoxy group-containing resins, and polymerizable unsaturated monounsaturated monomers containing acrylic acid or methacrylic acid. Epoxy acrylate resins obtained by reacting body components with epoxy groups of various epoxy group-containing resins, and urethanes obtained by reacting polyisocyanate compounds, polyol compounds, and epoxy group-containing resins having hydroxyl groups An ester-modified epoxy group-containing resin, a polyoxyalkylene-modified epoxy group-containing resin obtained by reacting a polyoxyalkylene compound with an epoxy group-containing resin having a hydroxyl group, and the like.

As a phenol resin, a novolak-type resin and a resol-type resin are mentioned, Preferably it is a resol-type resin, and it is preferable to use together with an epoxy resin.

Siloxane resins are curable resins such as ladder type, random type, cage type, ladder type and the like which are bonded to one or more siloxane bonds and are not included in the scope of the patent application of the present invention. Examples include: alkoxy-containing resins siloxane, siloxane containing silanol group, siloxane containing (meth)acrylic group, siloxane containing epoxy group, siloxane containing mercapto group, siloxane containing amine group, Siloxane containing styryl group, siloxane containing isocyanate group, siloxane containing urea group, siloxane containing vinyl group, siloxane containing thioether group, etc. These reactive functional groups may exist alone or in a mixture of two or more.

As the polyimide resin, a resin derived from an acid anhydride and an aromatic diamine, a resin derived from an acid anhydride and an aliphatic diamine, or two or more of these resins can be used in combination. When there are multiple resin layers, in order to It is preferably a transparent polyimide resin so as not to impair the appearance of the base layer or the substrate. Pyromellitic Dianhydride (PMDA), Naphthalene-2,3,6,7-Tetracarboxylic Dianhydride (NTCDA), 3,3' ,4,4'-Biphenyltetracarboxylic dianhydride (3,3',4,4'-Biphenyltetracarboxylic Dianhydride, BPDA), cyclohexanetetracarboxylic dianhydride, phenylene bis(trimellitic acid monoester) anhydride), 4,4'-oxydiphthalic dianhydride, benzophenone-3,4,3',4'-tetracarboxylic dianhydride, diphenyl-3,4,3' ,4'-tetracarboxylic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 4,4'-(2,2'-hexafluoroisopropylidene)diphthalic dianhydride Wait. On the other hand, as diamines, m-phenylenediamine, p-phenylenediamine, 2,4-diaminotoluene, 4,4'-diaminodiphenyl ether, 1,3-bis(4 -aminophenoxy)benzene, 4,4'-diaminodiphenyl benzene, 2,2-bis(4-aminobenzyloxyphenyl)propane, bis[4-(4-amino) phenoxy) phenyl] benzene, 4,4'-diaminobenzylaniline, 9,9-bis(4-aminophenyl) benzene and the like.

In the layered product of the present invention, it is preferable to use a photopolymerization initiator, a photoacid generator, In the case of thermal curing, the photobase generator is preferably a thermal polymerization initiator, thermal acid generator, amine-based curing agent, caprolactone-based curing agent, or the like used in combination. As a compounding quantity of these hardening accelerators, 0.1 weight part - 20 weight part are preferable with respect to 100 weight part of resin compositions, and 0.1 weight part - 10 weight part are desirable.

The resin composition used for the resin layer is supposed to be dissolved in a solvent and applied to a substrate or the like as a solution to form a layer, and then cured.

Examples of the solvent include organic solvents for the purpose of adjusting the solid content concentration, improving dispersion stability, improving coating properties, and improving adhesion to substrates. For example, examples of alcohols include methanol, ethanol, butanol, isobutanol, isopropanol, propanol, 3rd butanol, 2nd butanol, and benzyl alcohol; and examples of ketones include acetone and methyl ethyl alcohol. base ketone, methyl isobutyl ketone, diisobutyl ketone, cyclohexanone, diacetone alcohol; as esters, ethyl acetate, methyl acetate, butyl acetate, 2-butyl acetate, methyl acetate Oxybutyl ester, amyl acetate, propyl acetate, isopropyl acetate, ethyl lactate, methyl lactate, butyl lactate; as ethers, isopropyl ether, methyl cellosolve, ethyl cellosolve can be exemplified ethylene glycol, diethylene glycol, triethylene glycol, and propylene glycol; as glycol esters, ethylene glycol monoethyl ether acetate, methoxypropane Ethyl carbitol acetate, butyl carbitol acetate, ethyl carbitol acetate; as glycol ethers, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, butyl diethylene glycol Alcohol, methyl triethylene glycol, 1-methoxy-2-propanol, propylene glycol monobutyl ether, 3-methoxy-3-methyl-1-butanol, diethylene glycol monohexyl ether, propylene glycol mono Methyl ether propionate, dipropylene glycol methyl ether, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, ethylene glycol diethyl ether, diethylene glycol diethyl ether; Xylene, n-hexane, cyclohexane, heptane; N-methyl-2-pyrrolidone, N,N-dimethylformamide, γ-butyrolactone, etc. are mentioned as another organic solvent. These organic solvents may be used alone or in combination of two or more.

Regarding the method of forming the resin layer on the substrate, various resin solutions can be applied. After the liquid is dried, it is formed by either heating or active energy ray irradiation. As curing conditions, it is sufficient to form a crosslink to such an extent that cloudiness or elution does not occur in the hard coat film forming step to be applied later, and it is preferable that the crosslink is not completely formed.

As a method of forming a resin layer, a casting method, a roll coating method, a bar coating method, a spray coating method, an air knife coating method, a spin coating method, a flow coating method, a curtain coating method, and a dipping method are mentioned, for example. In addition, the coating film thickness is adjusted by the solid content concentration in consideration of the formed film thickness after drying and hardening.

For the purpose of improving flexibility, adhesiveness, or the like, a thermoplastic resin, rubber particles, or the like may be mixed in the resin layer. As a compounding amount, it is desirable to mix|blend in the range which does not impair the curability of a curable resin, and it is preferable that it is 0 weight part - 50 weight part of thermoplastic resins with respect to 100 weight part of curable resins.

In the layered product of the present invention, the substrate may be surface-treated to form a surface-treated layer. The surface treatment of the base material is performed for the purpose of imparting adhesiveness by chemical bonding with the resin layer or the resin layer, electrostatic bonding, or a tackifying effect due to unevenness. Common tackifying treatments, Coupling agent treatment, ultraviolet irradiation treatment, plasma treatment, corona discharge treatment, sandblasting treatment, brush treatment, grinding treatment, etching treatment, chemical conversion treatment, anodization, etc.

When the base material is a resin, the resin base material may be subjected to various wirings, such as a thin film coating of an inorganic material that imparts metallic luster, or an electronic circuit, as necessary.

The layered product of the present invention is provided with a hard coat film containing a hard siloxane resin layer on the surface, and is therefore excellent in scratch resistance and transparency, and can be formed by air curing in a short time, so it can be applied to various applications. For example, it can be applied to touch Panels, conductive films, anti-reflection films, reflective films, diffusion films, anti-scattering films, protective films, front panels, housings, buttons, sensors and other displays or electronic device components, or windows, instrument panels, interior and exterior decorations , partition windows, windshields, headlights, capacitors, insulating film, hot wire shielding film, decoration. Vehicle components such as transfer films, doors or surface components of furniture, decorative materials for floors, doors, window frames, windows, walls, door handles, roofs, door floors, tiles, bridges, waterproof sheets, window films, dimming films, etc. Construction or civil engineering components; optical components such as lenses or polarizers, wavelength conversion elements, sensors, or buttons or surface components of home appliances, or energy-related components such as solar cells or wind power generation, fuel cells, and piezoelectric films; buffer coatings Layers, non-conductive films, cover films, release films, resist layers and other semiconductor components, or cards, inkjet paper, thermal paper, marking films, design films, signboards, advertisements, decorative materials, signs, stamps Machine supplies, recording or graphic components of copier rollers, heat sealers, etc., or kitchens such as kitchen counters, sinks, dressing tables, surrounding walls or ceilings of bathtubs. Sanitary components, or various hard coatings used indoors and outdoors.

[Example]

Hereinafter, the present invention will be described in more detail based on Examples and Comparative Examples, but the present invention is not limited to the following Examples.

Synthesis Example 1

1.2 g (1.9 mmol) of 1,3,5-tris(trimethoxysilylpropyl)isocyanurate (Shin-Etsu Chemical Co., Ltd.) was placed in a reaction vessel equipped with a stirrer, a dropping funnel, and a thermometer. Manufacturing: KBM9659) and 26.0 g (0.1 mol) of 3-glycidyloxypropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd.: KBM-403) were added together With stirring, 6.4 g of a 0.05% hydrochloric acid aqueous solution (amount of water: 1 mole of the hydrolyzable group) was put into the dropping funnel, and added while stirring at room temperature. After the completion of the dropwise addition, the temperature was raised to 60° C. and stirred for 1 hour. Then, 11 g of Propylene Glycol Monomethyl Ether (PGME) was added for cooling to obtain a solution (siloxane) of the partially hydrolyzed condensate that was the target. Resin solution A1). The epoxy equivalent of the obtained partially hydrolyzed condensate was 220.

Synthesis Example 2

16.5 g (0.027 mol) of KBM9659, 1.0 g (0.004 mol) of KBM-403, and 5.9 g of PGME were added to a reaction vessel equipped with a stirrer, a dropping funnel, and a thermometer, and the solution was stirred. 4.7 g of 0.05% hydrochloric acid aqueous solution was put into the funnel, and it was added while stirring at room temperature. After completion of the dropwise addition, the temperature was raised to 60° C. and stirred for 1 hour, followed by cooling to obtain a target siloxane condensate (siloxane resin solution A2). The epoxy equivalent of the obtained reactant was 3890.

Synthesis Example 3

21.7 g (0.035 mol) of KBM9659 and 2.5 g (0.1 mol) of KBM-403 were put into a reaction vessel equipped with a stirrer, dropping funnel, and a thermometer, and stirred, and 11.6 g of 0.05 mol was put into the dropping funnel. % aqueous hydrochloric acid was added at room temperature while stirring. After completion of the dropwise addition, the temperature was raised to 60° C. and stirred for 1 hour. Then, 17.6 g of PGME was added for cooling to obtain a target siloxane condensate (siloxane resin solution A3). The obtained reactant had an epoxy equivalent weight of 422 and a molecular weight of 43600.

Synthesis Example 4

30.0 g (0.12 moles) of 3-methacryloyloxypropyltrimethoxysilane (XIAMETER OFS6030: manufactured by Toray Dow Corning) was put into a reaction vessel equipped with a stirrer, a dropping funnel, and a thermometer. ), put 9.3 g of a 0.05% hydrochloric acid aqueous solution into the dropping funnel, and add it while stirring at room temperature. After completion of the dropwise addition, the temperature was raised to 60° C. and stirred for 1 hour. Then, 5.8 g of PGME was cooled and added to obtain the target siloxane condensate (siloxane resin solution A4, molecular weight 1000).

Example 1 to Example 4 and Comparative Example 1

The siloxane resin solution A1 to the siloxane resin solution A4 obtained in the synthesis example, the polymerization initiator and the solvent were prepared in the proportions (parts by weight) shown in Table 1 to obtain a siloxane-based curable resin Composition (hard coating liquid) H1 to siloxane-based curable resin composition (hard coating liquid) H5.

Here, CPI-100 (San Apro) used as a hardening catalyst is a photoacid generator, WPBG-266 (Wako Pure Chemical Industries) is a photobase generator, SI-80 (Sanxin Chemical Industry Co., Ltd.) ) is a cationic polymerization initiator, Irg184 (BASF) is a radical photopolymerization initiator, and the solvent is PGME.

Formation and evaluation of hard coat film

The siloxane-based curable resin composition (hard coating liquid) H1, the siloxane-based curable resin composition (hard coating liquid) H2, the siloxane-based curable resin composition (hard coating liquid) H2, and the The siloxane-based curable resin composition (hard coating liquid) H3 and the siloxane-based curable resin composition (hard coating liquid) H5 were coated on a PET substrate (thickness 100 μm, length 10 cm, width 10 cm), After drying at 80°C for 6 minutes, it was cooled at room temperature for 5 minutes. Then, in an oxygen atmosphere, using a high pressure mercury lamp of 2 kW/cm ² , a film was formed at a cumulative exposure amount (365 nm conversion) of 400 mJ/cm ² .

The siloxane-based curable resin composition (hard coating solution) H4 of Example 4 was coated on a PET substrate (thickness 100 μm, length 10 cm, width 10 cm) by spin coating, and dried at 80° C. After 6 minutes, it was further heated at 100° C. for 30 minutes to form a film.

Evaluation of hard coat films

[Scratching resistance test 1]

The back-and-forth test was performed 10 times under a load of 1.0 kg using #0000 steel wool on the film test piece on which the hard coat film was formed, and the number of scratches was visually evaluated.

○: 0 or more scratches and less than 5 scratches

△: 5 or more scratches and less than 10 scratches

×: 10 or more scratches

[adhesion]

For the film test piece on which the hard coat film was formed, use a razor blade on the coating film with 2 11 vertical and horizontal incisions were made at mm intervals to form 100 grids. After attaching the scotch tape, the presence or absence of peeling when peeled off suddenly at an angle of 60 degrees was visually observed. Count/100 squares to evaluate.

○: 0/100

×: 1/100~100/100

The results are shown in Table 2.

Synthesis Example 5

1.2 g (1.9 mmol) of 1,3,5-tris(trimethoxysilylpropyl)isocyanurate (Shin-Etsu Chemical Co., Ltd.) was placed in a reaction vessel equipped with a stirrer, a dropping funnel, and a thermometer. Manufacturing: KBM9659) and 26.0 g (0.1 mol) of 3-glycidyloxypropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd.: KBM-403) were stirred, and 6.4 g of 0.05 % Aqueous hydrochloric acid solution (water content: 1 time mole of hydrolyzable group) was added while stirring at room temperature. After completion of the dropwise addition, the temperature was raised to 60° C. and stirred for 1 hour, followed by cooling and adding 11 g of propylene glycol monomethyl ether (PGME) to obtain a solution (siloxane resin solution A5) of the target partially hydrolyzed condensate. The epoxy equivalent of the partially hydrolyzed condensate obtained The amount is 1300.

Synthesis Example 6

1.1 g (1.8 mmol) of 1,3,5-tris(trimethoxysilylpropyl)isocyanurate (Shin-Etsu Chemical Co., Ltd.) was placed in a reaction vessel equipped with a stirrer, a dropping funnel, and a thermometer. Manufacturing: KBM9659) and 25.0 g (0.1 mol) of 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd.: KBM-303) were stirred, and added to a dropping funnel. 5.9 g of a 0.05% hydrochloric acid aqueous solution (water content: 1 time mole of the hydrolyzable group) was put into it, and it was added while stirring at room temperature. After completion of the dropwise addition, the temperature was raised to 60° C. and stirred for 1 hour, followed by cooling and adding 11 g of propylene glycol monomethyl ether (PGME) to obtain a solution (siloxane resin solution A6) of the target partially hydrolyzed condensate. The epoxy equivalent of the obtained partially hydrolyzed condensate was 1,000.

Example 5 to Example 14 and Comparative Example 2

The siloxane resin solution A5-siloxane resin solution A6, epoxy resin E1, photocationic polymerization initiator, surface conditioner and The solvent is used to obtain a siloxane-based curable resin composition (hard coating liquid) H6 to a siloxane-based curable resin composition (hard coating liquid) H16.

The notation of Table 3 is shown.

A5: 3-glycidoxypropyl-containing siloxane co-condensate obtained in Synthesis Example 5

A6: 2-(3,4-epoxycyclohexyl)ethyl-containing siloxane co-condensate obtained in Synthesis Example 6

E1: Epoxy resin: Celloxide 2021P (made by Daicel)

IK-1: Diaryl iodonium. (Rf) _n PF _6-n salt (manufactured by San Apro)

WPI170: Diaryl iodo. PF ₆ salt (manufactured by Wako Pure Chemical Industries, Ltd.)

WPI116: Diaryl iodo. SbF ₆ salt 50% propylene carbonate solution (manufactured by Wako Pure Chemical Industries, Ltd.)

CPI100P: Triaryl scorpion. PF ₆ salt 50% propylene carbonate solution (manufactured by San Apro)

CPI101A: Triaryl scorpion. SbF ₆ salt 50% propylene carbonate solution (manufactured by San Apro)

R43: fluorine-containing group. Oligomer containing lipophilic group (manufactured by DIC)

KF6003: Methanol-modified dimethylsiloxane (manufactured by Shin-Etsu Chemical Industry Co., Ltd.)

BYK375: Polyetherester modified hydroxyl-containing polydimethylsiloxane (manufactured by BYK)

BYK377: Polyether-modified hydroxyl-containing polydimethylsiloxane (manufactured by BYK)

PGME: 1-methoxy-2-propanol (manufactured by Kanto Chemical Co., Ltd.)

Formation of hard coat film

The siloxane-based curable resin compositions H6 to siloxane-based curable resin compositions H16 obtained in Examples 5 to 14 and Comparative Example 2 were coated on PET substrates ( 100 μm in thickness, 10 cm in length, 10 cm in width), dried at 80° C. for 6 minutes, and then cooled at room temperature for 5 minutes. Then, in an oxygen atmosphere, using a high pressure mercury lamp of 2 kW/cm ² , a film was formed at a cumulative exposure amount (365 nm conversion) of 400 mJ/cm ² to obtain a film test piece with a film thickness of 10 μm.

Evaluation of hard coat films (film test pieces)

[yellowness]

The film test piece was measured using an ultraviolet-visible spectrophotometer (UV-VIS SPECTROPHOTOMETER) UV-3600Plus (manufactured by Shimadzu Corporation) with reference to a PET substrate.

[Scratching resistance test 1]

as above.

[Scratch resistance test 2]

The film test piece was subjected to 10 reciprocating tests using #0000 steel wool under a load of 1.5 kg, and the number of scratches was visually evaluated.

○: 0 scratches

×: 1 or more scratches

The results are shown in Table 4.

Next, the Example of the laminated body which used the siloxane-type curable resin composition of the claim of this invention as a hard-coat liquid and formed a hard-coat film on various base materials is described.

Synthesis Example 7

2.5 g (4.0 mmol) of 1,3,5-tris(trimethoxysilylpropyl)isocyanurate (Shin-Etsu Chemical Co., Ltd.) was placed in a reaction vessel equipped with a stirrer, a dropping funnel, and a thermometer. Manufacturing: KBM9659) and 26.0 g (0.1 mol) of 3-glycidyloxypropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd.: KBM-403) were stirred, and 6.7 g of 0.05 % Aqueous hydrochloric acid solution (water content: 1 time mole of hydrolyzable group) was added while stirring at room temperature. dropwise After the completion, the temperature was raised to 60° C. and stirred for 1 hour. Then, 11 g of propylene glycol monomethyl ether (PGME) was cooled and added to obtain a solution (siloxane resin solution A7) of the target partially hydrolyzed condensate. The epoxy equivalent of the obtained partially hydrolyzed condensate was 220.

Synthesis Example 8

2.5 g (4.0 mmol) of 1,3,5-tris(trimethoxysilylpropyl)isocyanurate (Shin-Etsu Chemical Co., Ltd.) was placed in a reaction vessel equipped with a stirrer, a dropping funnel, and a thermometer. Manufacturing: KBM9659) and 26.0 g (0.1 mol) of 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd.: KBM-303) were stirred, and added to a dropping funnel. 6.7 g of a 0.05% hydrochloric acid aqueous solution (water content: 1 time mole of the hydrolyzable group) was put into it, and added while stirring at room temperature. After completion of the dropwise addition, the temperature was raised to 60° C. and stirred for 1 hour, followed by cooling and adding 11 g of propylene glycol monomethyl ether (PGME) to obtain a solution (siloxane resin solution A8) of the target partially hydrolyzed condensate. The epoxy equivalent of the obtained partially hydrolyzed condensate was 250.

Synthesis Example 9

30.0 g (0.12 moles) of 3-methacryloyloxypropyltrimethoxysilane (XIAMETER OFS6030: manufactured by Toray Dow Corning) was put into a reaction vessel equipped with a stirrer, a dropping funnel, and a thermometer. ), put 9.3 g of a 0.05% hydrochloric acid aqueous solution into the dropping funnel, and add it while stirring at room temperature. After completion of the dropwise addition, the temperature was raised to 60° C. and stirred for 1 hour, and then 5.8 g of PGME was added for cooling to obtain the target siloxane condensate (siloxane tree). lipid solution A9).

Preparation Example 1 to Preparation Example 5

The siloxane resin solution A7 to the siloxane resin solution A9, the polymerization initiator and the solvent obtained in the synthesis example were prepared in the proportions (parts by weight) shown in Table 5 to obtain a siloxane-based curable resin Composition (hard coating solution) H17~Siloxane-based curable resin composition (hard coating solution) H21.

Here, WPI-116 (manufactured by Wako Pure Chemical Industries, Ltd.) used as a hardening catalyst is a photoacid generator, WPBG-266 (manufactured by Wako Pure Chemical Industries, Ltd.) is a photobase generator, and SI-80 (manufactured by Sanshin Chemical Industry Co., Ltd.) manufacture) is a cationic polymerization initiator, Irg184 (manufactured by IGM) is a radical photopolymerization initiator, and the solvent is PGME.

Preparation of resin agent

30 parts by weight of dimethylol-tricyclodecane diacrylate (manufactured by Kyeisha Chemical Co., Ltd.: Light acrylate DCP-A) and 70 parts by weight of pentaerythritol triacrylate hexamethylene diacrylate were prepared Isocyanate urethane prepolymer (Kyoeisha Chemical Co., Ltd.: UA-306H), 3 parts by weight of bis(2,4,6-trimethylbenzyl)-phenylphosphine oxide (BASF Japan) as a polymerization initiator ) company; Irgacure 819), and 333 parts by weight of propylene glycol monomethyl ether as a solvent to obtain a resin composition (P-1).

Preparation of Surface Treatment Agent

A surface treatment composition (S-1) was obtained by mixing 30 parts by weight of aminosilane-based coupling agent KBP-40 (manufactured by Shin-Etsu Chemical Co., Ltd.), 35 parts by weight of ethanol as a solvent, and 35 parts by weight of water.

Example 15

The hard coating solution H17 obtained in Preparation Example 1 was coated on a PET substrate (thickness 100 μm, length 10 cm, width 10 cm) by spin coating, dried at 80° C. for 6 minutes, and then cooled at room temperature 5 minutes. Then, in an oxygen atmosphere, a high-pressure mercury lamp of 2kW/ ^cm2 was used to form a film with a cumulative exposure amount of 1000mJ/ ^cm2 (365nm conversion) to obtain a hard coat (HC) film formed on the surface of the PET substrate. PET laminate with HC coating.

Example 16, Example 17, Comparative Example 3

Except having made the hard coating liquid into the composition shown in Table 6, it carried out similarly to Example 15, and obtained the HC film-coated PET laminated body which formed the hard coating film on the PET base material surface.

Example 18

The hard coating solution H20 obtained in Preparation Example 4 was coated on a PET substrate (thickness 100 μm, length 10 cm, width 10 cm) by spin coating, and dried at 80°C. After drying for 6 minutes, the film was further heated at 100° C. for 30 minutes to form a film to obtain a HC-coated PET laminate in which a hard coat film was formed on the surface of the PET substrate.

Example 19

The coating solution of the resin composition (P-1) was coated on a PC substrate (thickness 3mm, length 10cm, width 10cm) by spin coating, dried at 80°C for 6 minutes, and then dried at room temperature. Cool for 5 minutes. Then, in an oxygen atmosphere, a resin layer was formed into a film at a cumulative exposure amount (365 nm conversion) of 100 mJ/cm ² using a high pressure mercury lamp of 2 kW/cm ² . Next, the hard coating liquid H17 obtained in Preparation Example 1 was applied on the resin layer by spin coating, dried at 80° C. for 6 minutes, and then cooled at room temperature for 5 minutes. Then, in an oxygen atmosphere, a high pressure mercury lamp of 2kW/ ^cm2 was used to form a film with a cumulative exposure amount of 1000mJ/ ^cm2 (365nm conversion) to obtain a hard coat film on the PC substrate through the resin layer. The resulting PC laminate with HC coating.

Example 20

The solution of the surface treatment agent (S-1) was apply|coated to the aluminum plate by the spin coating method, and the aluminum plate was surface-treated, and it dried at 100 degreeC for 5 minutes. Next, the hard coating liquid H17 obtained in Preparation Example 1 was applied on the resin layer by spin coating, dried at 80° C. for 6 minutes, and then cooled at room temperature for 5 minutes. Then, in an oxygen environment, using a high-pressure mercury lamp of 2kW/ ^cm2 , a film was formed with a cumulative exposure amount of 1000mJ/ ^cm2 (365nm conversion) to obtain a hard coating film formed on the surface-treated aluminum substrate. of aluminum laminates with HC coating.

Example 21

The hard coating solution H17 obtained in Preparation Example 1 was coated on an aluminum substrate (thickness 500 μm, length 10 cm, width 10 cm) by spin coating, dried at 80° C. for 6 minutes, and then cooled at room temperature 5 minutes. Then, in an oxygen atmosphere, a high-pressure mercury lamp of 2kW/ ^cm2 was used to form a film with a cumulative exposure amount of 1000mJ/ ^cm2 (365nm conversion) to obtain a hard coat film formed on an aluminum substrate with HC. Coated aluminum laminate.

Evaluation of hard coat films

[Scratching resistance test 1]

The back-and-forth test was performed 10 times under a load of 1.0 kg using #0000 steel wool on the film test piece on which the hard coat film was formed, and the number of scratches was visually evaluated.

○: No scratches

×: 1 or more scratches

[adhesion]

For the film test piece on which the hard coat film was formed, a razor blade was used to cut 11 vertical and horizontal incisions at 2 mm intervals in the coating film to form 100 grids, and after adhering the scotch tape, it was observed visually. The presence or absence of peeling when peeled off sharply at an angle of 60 degrees was evaluated as the number of peeled grids/100 grids.

○: 0/100

△: 1/100~50/100

×: 50/100~100/100

The results are shown in Table 6.

[Table 6]

[Industrial Availability]

The siloxane-based curable resin composition of the present invention can be widely used as a coating material, a hard coating material, and the like excellent in scratch resistance, transparency, and the like. The composition and the hard coating liquid can be widely used as various hard coating materials such as electronic components such as displays and housings, interiors of automobiles, household electrical appliances, and building components, for example.

By using the siloxane-based curable resin composition of the present invention as a hard coating solution, atmospheric hardening in a short time can be achieved, and it can be provided on the surface of the substrate through another resin layer as necessary to form a hard coating. A layered product consisting of a hard siloxane resin layer of the coating. The laminate can be applied to, for example, electronic equipment parts such as displays and housings, vehicle parts such as interiors and windows, furniture and building parts, optical parts such as lenses, surface parts of home appliances, energy-related parts such as solar cells, and buffer coatings. Such as semiconductor components, graphic components such as recording components and design films, sanitary components such as kitchen counters and dressing tables, etc., and various hard coatings used indoors and outdoors.

Claims (16)

A siloxane-based curable resin composition, characterized in that it comprises a partially hydrolyzed condensate of the following components (A) and (B), and the epoxy equivalent of the partially hydrolyzed condensate is 200 to 4000 (g/eq ): (A) component, an alkoxysilane having an isocyanurate ring structure represented by the following general formula (i) or its partial hydrolysis condensate;

(In the formula, R ¹ represents an organic group with 1 to 15 carbon atoms, R ² represents a hydrogen atom or an alkyl group with 1 to 5 carbon atoms, R ³ represents an organic group with 1 to 6 carbon atoms, and a represents a number of 0 to 2. , X independently represents a hydrogen atom, a hydrocarbon group having 1 to 15 carbon atoms or a silyl alkyl group represented by the formula (ii))

(In the formula, R ¹ to R ³ and a have the same meanings as in the above formula (i)) (B) component, an alkoxy group having an epoxy group or an oxetanyl group represented by the following formula (iii) silane or its partial hydrolysis condensate; R ⁴ _b R ⁵ _c Si(OR ⁶ ) _4-bc (iii) (in the formula, R ⁴ and R ⁵ are directly bonded to Si, and R ⁴ represents an epoxy group Or an organic group with a carbon number of 1 to 10 in an oxetanyl group, R ⁵ represents an organic group with a carbon number of 1 to 10 that does not contain an epoxy group and an oxetanyl group, and R ⁶ represents a hydrogen atom or carbon For the alkyl groups of numbers 1 to 5, b and c represent numbers of 0<b≦1 and 0≦c≦2, respectively, and b+c represent numbers of 0<b+c≦2). The siloxane-based curable resin composition according to claim 1, wherein the ratio of the (A) component to the (B) component is 0.01 mol of the (A) component with respect to 1 mol of the (B) component ~7 moles. The siloxane-based curable resin composition according to claim 1, which is a hard coating liquid containing a curing catalyst as the component (C) and an organic solvent as the component (D). A siloxane-based curable resin composition, characterized by comprising: a partially hydrolyzed condensate of the following (A) components and (B) components, a photocationic polymerization initiator of (C') components, and (E) components The surface conditioner, the epoxy equivalent of the partially hydrolyzed condensate is 200 to 4000 (g/eq): (A) component, an alkane having an isocyanurate ring structure represented by the following general formula (i) Oxysilanes or their partially hydrolyzed condensates;

(In the formula, R ¹ represents an organic group with 1 to 15 carbon atoms, R ² represents a hydrogen atom or an alkyl group with 1 to 5 carbon atoms, R ³ represents an organic group with 1 to 6 carbon atoms, and a represents a number of 0 to 2. , X independently represents a hydrogen atom, a hydrocarbon group having 1 to 15 carbon atoms or a silyl alkyl group represented by the formula (ii))

(In the formula, R ¹ to R ³ and a have the same meanings as in the above formula (i)) (B) component, an alkoxy group having an epoxy group or an oxetanyl group represented by the following formula (iii) silane or its partial hydrolysis condensate; R ⁴ _b R ⁵ _c Si(OR ⁶ ) _4-bc (iii) (in the formula, R ⁴ and R ⁵ are directly bonded to Si, and R ⁴ represents an epoxy group Or an organic group with a carbon number of 1 to 10 in an oxetanyl group, R ⁵ represents an organic group with a carbon number of 1 to 10 that does not contain an epoxy group and an oxetanyl group, and R ⁶ represents a hydrogen atom or carbon Alkyl groups of numbers 1 to 5, b and c represent numbers of 0<b≦1, 0≦c≦2, respectively, b+c represent numbers of 0<b+c≦2) (C’) component, photocationic polymerization A starting agent; (E) component, a surface conditioner containing a fluorine compound, a dimethylsiloxane compound, or a modified body or derivative thereof. The siloxane-based curable resin composition according to claim 4, wherein the component (E) is a reactive group having a reactive group that forms a covalent bond with the partially hydrolyzed condensate of the component (A) and the component (B). surface conditioner. A method for forming a hard coat film, characterized in that: after applying the siloxane-based curable resin composition as described in item 1 or item 4 of the patent application scope on a base layer or a base material and drying, It is hardened by active energy ray irradiation. The method for forming a hard coat film according to claim 6, wherein heat treatment is further performed after curing. A cured film obtained by curing the siloxane-based curable resin composition as described in claim 1 or claim 4. A layered product comprising a hard siloxane resin layer and a base material layer, wherein the hard siloxane resin layer is composed of a siloxane-based curable resin, a hardening catalyst as the component (C), and a D) The hard coating liquid of the organic solvent of the component is formed, and the siloxane-based curable resin contains the partial hydrolysis condensate of the following (A) component and (B) component, and the epoxy equivalent of the partially hydrolyzed condensate is 200~4000 (g/eq); (A) component, the alkoxysilane with isocyanurate ring structure represented by the following general formula (i) or its partial hydrolysis condensate;

(In the formula, R ¹ represents an organic group with 1 to 15 carbon atoms, R ² represents a hydrogen atom or an alkyl group with 1 to 5 carbon atoms, R ³ represents an organic group with 1 to 6 carbon atoms, and a represents a number of 0 to 2. , X independently represents a hydrogen atom, a hydrocarbon group having 1 to 15 carbon atoms or a silyl alkyl group represented by the formula (ii))

(In the formula, R ¹ to R ³ and a have the same meanings as in the above formula (i)) (B) component, an alkoxy group having an epoxy group or an oxetanyl group represented by the following formula (iii) silane or its partial hydrolysis condensate; R ⁴ _b R ⁵ _c Si(OR ⁶ ) _4-bc (iii) (in the formula, R ⁴ and R ⁵ are directly bonded to Si, and R ⁴ represents an epoxy group Or an organic group with 1 to 10 carbon atoms of an oxetanyl group, R ⁵ represents an organic group with 1 to 10 carbon atoms that does not contain an epoxy group and an oxetanyl group, and R ⁶ represents a hydrogen atom or carbon For the alkyl groups of numbers 1 to 5, b and c represent numbers of 0<b≦1 and 0≦c≦2, respectively, and b+c represent numbers of 0<b+c≦2). The laminate according to claim 9, wherein the hard siloxane resin layer and the base material are laminated with a single or multiple resin layer interposed therebetween. The layered product according to claim 9, wherein the layers are layered with the surface treatment layer of the base material interposed therebetween. The laminate according to claim 10, wherein the resin layer is a combination of acrylic resin, urethane resin, polyurea resin, epoxy resin, phenol resin, siloxane resin, polyimide resin, It is composed of one or two or more of polyimide imide resins alone. The layered product according to claim 11, wherein the surface treatment layer of the substrate is treated with a treatment selected from the group consisting of tackifying treatment, coupling agent treatment, ultraviolet irradiation treatment, plasma treatment, corona discharge treatment, sandblasting treatment, brush treatment It is formed by treatment, polishing treatment, etching treatment, chemical conversion treatment, and treatment in anodizing. The laminate according to claim 9, wherein the base material is any one of thermoplastic resin, curable resin, metal, wood, paper, glass, and stone. A method for manufacturing a layered product, characterized in that: the layered product as described in item 9 of the scope of the application is produced, and the method is to apply a hard coating solution on a substrate, dry it, and use active energy Hardening by irradiation or heating. The method for producing a layered product according to claim 15, wherein the method is produced by any method selected from the group consisting of flow coating, roll coating, bar coating, spray coating, spin coating, curtain coating and dipping. Apply hardcoat.