JP2022025028A - Laminate - Google Patents

Abstract

To provide a laminate which has excellent wear resistance and significantly improved durability against a weathering test.SOLUTION: The laminate includes a substrate layer, a cured layer (P layer) of an acrylic resin composition, and a cured layer (T layer) of an organosiloxane resin composition in this order. The acrylic resin composition contains at least 70 mol% of a repeating unit represented by the following formula (A) (where X represents at least one selected from the group consisting of a hydrogen atom and a methyl group; and Y represents at least one group selected from the group consisting of a C1-4 alkyl group, a C5-12 cycloalkyl group and a C2-5 hydroxyalkyl group) and contains an amino-based silane coupling agent.SELECTED DRAWING: None

Description

The present invention relates to a laminate. More specifically, the present invention relates to a laminate having an acrylic resin layer and an organosiloxane resin layer on a plastic base material layer and having excellent wear resistance and weather resistance.

Plastic materials are used in various applications by taking advantage of their features such as impact resistance, light weight, and workability. In particular, acrylic resin, polycarbonate resin, styrene resin and the like, which are highly transparent plastics, are widely used as substitutes for glass. However, it is known that these resins do not have sufficient weather resistance and are decomposed and deteriorated in long-term outdoor use, resulting in impaired physical properties and appearance. In addition, these resins have drawbacks such as poor wear resistance, easy surface scratches, and easy attack by solvents.

In recent years, there has been a movement to apply a transparent plastic sheet as organic glass to window glass, especially automobile window glass, by taking advantage of its light weight and safety. When a plastic sheet is applied to such an application, it is required to have a high degree of weather resistance comparable to that of glass. Further, it is necessary to prevent scratches from occurring when the wiper is operated on the front glass, and it is necessary to prevent scratches from occurring when the window is raised and lowered in the side window. Such applications require a high level of wear resistance. In addition, sunroofs are expected to reach significant temperatures in the hot summer sun, and the plastic sheets used in this application are required to be more durable in changing environments and in high temperature environments.

For the purpose of improving these drawbacks, the surface of the plastic sheet has been conventionally provided with a thermosetting acrylic resin layer, and a siloxane-based cured film is coated on the layer to improve weather resistance, durability, and abrasion resistance. Proposals have been made (for example, Patent Documents 1 and 2).

For example, in Patent Document 1, a thermosetting acrylic resin layer containing a triazine-based ultraviolet absorber having a low photodecomposition rate and an acrylic polymer having a cyclohexyl group having a low polarity on the surface of a plastic sheet is provided. The provided laminate has been proposed. In this Patent Document 1, a weather resistance test (UV irradiation intensity 180 W / m ² , black panel temperature 63 ° C., 18 minutes out of 120 minutes) using Super Xenon Weather Meter SX-75 manufactured by Suga Testing Machine Co., Ltd. is 3000. After a time exposure test, the test piece was taken out, the surface was lightly rubbed and washed with a sponge soaked in a neutral detergent, and then the yellowness change (ΔYI) and haze change (ΔH) before and after the test were evaluated). It is disclosed that both ΔH do not increase much and show good weather resistance.

The above-mentioned Patent Document 1 was made by the present applicants, but as a result of further studies, it was found that the weather resistance is still not sufficient. In particular, good durability is desired even in a dew cycle weather resistance test in which a high-energy ultraviolet irradiation mode, a dark mode, and a dew condensation mode are repeated.

International Publication No. 2007/105741 Pamphlet Japanese Unexamined Patent Publication No. 2012-11142

Based on these circumstances, the present invention provides a laminate having excellent wear resistance and significantly improved durability against a dew cycle weather resistance test in which a high-energy ultraviolet irradiation mode, a dark mode, and a dew condensation mode are repeated. The purpose is to get.

The present inventors have made diligent efforts to put a predetermined amount of metal oxide on the cured layer of the acrylic resin composition containing an acrylic copolymer having a hydroxyalkyl group and a cycloalkyl group and an amino-based silane coupling agent. We have found that the above problems can be solved by forming a cured layer of the contained organosiloxane composition, and have reached the present invention.

That is, the present invention is as follows.
[1] A laminate having a base material layer, a cured layer (P layer) of an acrylic resin composition, and a cured layer (T layer) of an organosiloxane resin composition in this order.
The acrylic resin composition is
(A) The following formula

(X in the formula (A) is at least one selected from the group consisting of a hydrogen atom and a methyl group, and Y is an alkyl group having 1 to 4 carbon atoms, a cycloalkyl group having 5 to 12 carbon atoms and a carbon number of carbon atoms. It is at least one group selected from the group consisting of 2 to 5 hydroxyalkyl groups, and the ratio of hydrogen atoms in X is 30 mol% or less, and the ratio of cycloalkyl groups in Y is 1 to 40 mol. %, The proportion of alkyl groups having 1 to 4 carbon atoms is 1 to 98 mol%, and the proportion of hydroxyalkyl groups having 2 to 5 carbon atoms is 1 to 15 mol%.)
Acrylic copolymer (component A) containing at least 70 mol% of the repeating unit represented by,
(B) It has a converted isocyanate group ratio of 5.5 to 50% by weight, and is 0.8 to 1.5 equivalents with respect to 1 equivalent of the hydroxy groups in the acrylic copolymer represented by the above formula (A). Amount of blocked polyisocyanate compound (B component),
(C) 0.001 to 0.4 parts by weight of the curing catalyst (C component) with respect to 100 parts by weight of the A component and B component in total, and (D) 100 parts by weight of the A component and B component in total. Contains 0.1 to 10 parts by weight of an amino-based silane coupling agent (component D) with respect to the portion.
The organosiloxane resin composition is
(E) Colloidal silica (E component), (F) Hydrolyzed condensate of alkoxysilane represented by the following formula (F) (F component), and R ¹ _m R ² _n Si (OR ³ ) _{4-m- n} (F)
In formula (F), R ¹ and R ² are independently selected from the group consisting of an alkyl group having 1 to 4 carbon atoms, a vinyl group, a methacryloxy group, an amino group, a glycidoxy group and a 3,4-epoxycyclohexyl group1. It is an alkyl group having 1 to 3 carbon atoms substituted with the above groups, R ³ is an alkyl group having 1 to 4 carbon atoms, and m and n are independently integers of 0, 1 and 2, respectively. And m + n is an integer of 0, 1, or 2.)
(G) Contains a metal oxide (G component),
The content of the E component is 10 to 60% by weight, the content of the F component is 40 to 90% by weight in terms of R ¹ _m R ² _n SiO _{(4-mn) / 2} , and the E A laminate in which the G component is 8 to 60% by weight with respect to 100 parts by weight of the total of the component and the F component.

[2] The laminate according to the above [1], which contains triazine-based ultraviolet absorber residues in Y in the above formula (A) in a proportion of 15 mol% or less.
[3] With respect to the acrylic resin composition, the following formula (H) of 1 to 40 parts by weight with respect to a total of 100 parts by weight of the A component and the B component.

(In the formula, R ⁴ is an alkyl group having 1 to 18 carbon atoms, a substituent represented by —CH ₂ CH (OH) CH _2OR ^{8 (where R 8 is} an alkyl group having 1 to 18 carbon atoms) or -CH (CH ₃ ) C (O) represents a substituent represented by O-R ⁹ (R ⁹ is an alkyl group having 1 to 18 carbon atoms), R ⁵ is a hydrogen atom and an alkyl group having 1 to 18 carbon atoms. Alternatively, it represents an alkoxy group having 1 to 18 carbon atoms, and R ⁶ and R ⁷ independently represent a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, an alkoxy group having 1 to 18 carbon atoms, or an alkoxy group having 1 to 18 carbon atoms. It represents a phenyl group which may be substituted with an alkyl group or a halogen atom, and V represents a hydrogen atom, an OH group or an alkyl group having 1 to 12 carbon atoms.
Contains the triazine-based ultraviolet absorber (H component) represented by the above, and the total content of the triazine-based ultraviolet absorber residue in the formula (A) and the H component is 1 to 40 parts by weight. The laminate according to [1] or [2].

[4] The laminate according to the above [1] to [3], wherein the content of the D component is 1.0 to 5.0 parts by weight with respect to a total of 100 parts by weight of the A component and the B component. body.
[5] The above-mentioned [1] to [4], wherein the C component is at least one compound selected from the group consisting of an organic tin compound, an organic titanium compound, an organic zirconium compound, a tertiary amine compound and a quaternary ammonium salt compound. The laminate described in.
[6] The laminate according to the above [1] to [5], wherein the content of the G component is 10 to 45 parts by weight with respect to a total of 100 parts by weight of the E component and the F component.
[7] The ratio of the content of the D component to the total 100 parts by weight of the A component and the B component and the content of the G component to the total 100 parts by weight of the E component and the F component is 15 to 200. The laminate according to the above [1] to [6].
[8] The laminate according to the above [1] to [7], wherein the G component is at least one metal oxide selected from the group consisting of titanium oxide, zinc oxide, cerium oxide, tin oxide and tungsten oxide.
[9] When the cumulative 50% particle size and the cumulative 90% particle size in the laser diffraction particle distribution measurement of the G component are D50 and D90, respectively, D90 is 100 nm or less and D90 / D50 is 20 or less. , The laminate according to the above [1] to [8].
[10] The laminate according to [8] or [9], wherein the amount of hydroxyl groups on the surface of the metal oxide (G component) is 3.5 to 5 / nm ² as measured by infrared absorption method.
[11] The laminate according to the above [1] to [10], wherein the base material layer is made of a thermoplastic resin. [12] A window glass formed from the laminate according to the above [1] to [11].

According to the present invention, it is possible to obtain a laminated body having excellent wear resistance and significantly improved durability against a dew cycle weather resistance test in which a high-energy ultraviolet irradiation mode, a dark mode, and a dew condensation mode are repeated. .. Therefore, it can be widely used as a high-performance resin glazing material for automobile windows and the like.

The laminate according to the present invention heat-reacts a base material layer, an acrylic resin cured layer (P layer, hereinafter may be simply referred to as an acrylic resin layer) formed by heat-reacting an acrylic resin composition, and an organosiloxane resin composition. It is an essential requirement that the siloxane resin cured layer (T layer, hereinafter simply referred to as siloxane resin layer) formed in this order is formed, but other layers may be laminated if necessary. Is also possible. As an example of the implementation, a laminate in which a silicon oxide layer by a PE-CVD method and a metal nanosheet on a scale are formed on a siloxane resin cured layer using an organosiloxane resin composition is exemplified.

In the present invention, it is an essential requirement that the acrylic resin cured layer (P layer) and the siloxane resin cured layer (T layer) are formed in this order on at least one side of the base material layer, but the other side. Layering on the layer is not always essential, and a preferable configuration is selected according to the application and need.

Hereinafter, each component constituting the laminate and the adjusting method according to the present invention will be specifically described in sequence.

<Acrylic resin composition>
The acrylic resin composition used in the present invention contains (A) an acrylic copolymer, (B) a blocked polyisocyanate compound, (C) a curing catalyst, and (D) an amino-based silane coupling agent. The components (A) to (D) will be described in detail.

<Acrylic copolymer (component A)>
The acrylic copolymer (hereinafter, may be referred to as component A) has the following formula (A).

An acrylic copolymer containing at least 70 mol%, preferably 80 mol%, more preferably 90 mol%, and particularly preferably 100 mol% of the repeating unit represented by.
In the formula, X is at least one selected from the group consisting of a hydrogen atom and a methyl group, and is preferably a methyl group. The proportion of hydrogen atoms is 30 mol% or less.
Y is at least one group selected from the group consisting of an alkyl group having 1 to 4 carbon atoms, a cycloalkyl group having 5 to 12 carbon atoms, and a hydroxyalkyl group having 2 to 5 carbon atoms.

Examples of the alkyl group having 1 to 4 carbon atoms include a methyl group, an ethyl group, a propyl group and a butyl group. Examples of the cycloalkyl group having 5 to 12 carbon atoms include a cyclopentyl group, a cyclohexyl group, and a cyclooctyl group. These groups may have a substituent such as a methyl group or an ethyl group. Examples of the hydroxyalkyl group having 2 to 5 carbon atoms include a hydroxyethyl group, a hydroxypropyl group, a hydroxybutyl group and a hydroxypentyl group. Examples of the alkylene group in the trialkoxysilyl group linked by the alkylene group having 2 to 5 carbon atoms include an ethylene group, a propylene group and a butylene group. Further, examples of the alkoxy group in the trialkoxysilyl group include a methoxy group and an ethoxy group.

When the total of the alkyl group having 1 to 4 carbon atoms, the cycloalkyl group having 5 to 12 carbon atoms, and the hydroxyalkyl group having 2 to 5 carbon atoms in Y is 100 mol%, the number of carbon atoms is 5 to 5. The proportion of 12 cycloalkyl groups is 1 to 40 mol%, the proportion of alkyl groups having 1 to 4 carbon atoms is 1 to 98 mol%, and the proportion of hydroxyalkyl groups having 2 to 5 carbon atoms is 1. ~ 15 mol%.

The Y may be a triazine-based ultraviolet absorber residue. In that case, the ratio of the triazine-based ultraviolet absorber residue is an alkyl group having 1 to 4 carbon atoms, a cycloalkyl group having 5 to 12 carbon atoms, a hydroxyalkyl group having 2 to 5 carbon atoms, and a triazine-based ultraviolet ray. When the total of the absorbent residues is 100 mol%, it is 0 to 15 mol%.

The acrylic copolymer preferably contains repeating units represented by the following formulas (A-1), (A-2) (A-3) and (A-4).

((A-1) unit)

In the formula (A-1), Y ¹ is an alkyl group having 1 to 4 carbon atoms, and is preferably a methyl group or an ethyl group. The repeating unit represented by the formula (A-1) is obtained by polymerizing methyl methacrylate and ethyl methacrylate. These can be used alone or in admixture.

The content of the unit of the formula (A-1) in the acrylic copolymer is 1 to 98 mol%, preferably 30 to 90 mol%, and more preferably 45 to 75 mol%. Above the lower limit, the flexibility is excellent and the siloxane resin layer is less likely to crack, which is preferable. Further, the value below the upper limit is preferable because the adhesion to the base material layer and the siloxane resin layer is excellent.

((A-2) unit)

In formula (A-2), X ¹ is a hydrogen atom or a methyl group, and Y ² is a cycloalkyl group having 5 to 12 carbon atoms. The repeating unit represented by the formula (A-2) is obtained by polymerizing an acrylate or methacrylate having at least one cycloalkyl group in the molecule. The cycloalkyl group has 5 to 12 carbon atoms. Specific examples thereof include a cyclohexyl group and a cyclooctyl group.

The repeating unit represented by the formula (A-2) can be introduced by copolymerizing the corresponding monomers. Specific examples of the corresponding monomers include cyclohexyl acrylate, 4-methylcyclohexyl acrylate, 2,4-dimethylcyclohexyl acrylate, 2,4,6-trimethylcyclohexyl acrylate, 4-t-butylcyclohexyl acrylate, adamantyl acrylate, and dicyclopentadi. Enyl acrylate, cyclohexylmethyl acrylate, 4-methylcyclohexylmethylacrylate, 2,4-dimethylcyclohexylmethylacrylate, 2,4,6-trimethylcyclohexylmethylacrylate, 4-t-butylcyclohexylmethylacrylate, cyclohexylmethacrylate, 4-methylcyclohexyl Methacrylate, 2,4-dimethylcyclohexylmethacrylate, 2,4,6-trimethylcyclohexylmethacrylate, 4-t-butylcyclohexylmethacrylate, adamantyl methacrylate, dicyclopentadienyl methacrylate, cyclohexylmethylmethacrylate, 4-methylcyclohexylmethylmethacrylate, 2 , 4-Dimethylcyclohexylmethylmethacrylate, 2,4,6-trimethylcyclohexymethylmethacrylate, 4-t-butylcyclohexylmethylmethacrylate and the like, and these can be used alone or in admixture of two or more. Among them, cyclohexyl methacrylate is preferably adopted.

The content of the (A-2) unit of the acrylic copolymer is 1 to 40 mol%, more preferably 5 to 40 mol%, still more preferably 8 to 35 mol%, and most preferably 12 to 32 mol%. Is. Above the lower limit, performance deterioration due to the influence of moisture can be reduced, which is preferable. Further, below the upper limit, the adhesion between layers is good, which is preferable.

((A-3) unit)

In the formula (A-3), X ² is a hydrogen atom or a methyl group, and Y ³ is a hydroxyalkyl group having 2 to 5 carbon atoms. Examples of the hydroxyalkyl group include a hydroxyethyl group, a hydroxypropyl group, a hydroxybutyl group and the like.

The repeating unit represented by the formula (A-3) can be introduced by copolymerizing the corresponding monomers. Specific examples of the corresponding monomers include 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, 3-hydroxypropyl acrylate, 3-hydroxypropyl methacrylate, 4-hydroxybutyl acrylate, and the like. Examples thereof include 4-hydroxybutyl methacrylate, 3-hydroxybutyl acrylate, 3-hydroxybutyl methacrylate, 2-hydroxybutyl acrylate, 2-hydroxybutyl methacrylate and the like, and these can be used alone or in combination of two or more. Of these, 2-hydroxyethyl methacrylate is preferably adopted.

The content of the (A-3) unit of the acrylic copolymer is 1 to 15 mol%, more preferably 5 to 15 mol%, still more preferably 8 to 15 mol%. Above the lower limit, sufficient heat resistance and weather resistance can be obtained, which is preferable. Further, below the upper limit, high heat resistance and water resistance can be realized, which is preferable.

((A-4) unit)

In the formula (A- ⁴ ), X3 is a hydrogen atom or a methyl group, and Y4 is a triazine ^- based ultraviolet absorber residue.
The repeating unit represented by the formula (A-4) can be introduced by copolymerizing an acrylate or methacrylate monomer having a triazine-based ultraviolet absorber residue. Specific examples of the acrylate or methacrylate monomer having an ultraviolet absorber residue include a repeating unit derived from an acrylic monomer represented by the following formula (A-4-a) or formula (A-4-b). It is preferably used.

(In the formula, R ¹¹ is an alkylene group having 2 to 6 carbon atoms, R ¹² represents a hydrogen atom, an alkyl group having 1 to 18 carbon atoms or an alkoxy group having 1 to 18 carbon atoms, and R ¹³ and R ¹⁴ are. The same or independently of each other, the phenyl may be substituted with a hydrogen atom, a halogen atom, an alkyl group having 1 to 18 carbon atoms, an alkoxy group having 1 to 18 carbon atoms, or an alkyl group or a halogen atom having 1 to 18 carbon atoms. A group is represented, R ¹⁵ represents an alkyl group having 1 to 18 carbon atoms, X ⁴ represents a hydrogen atom or a methyl group, and V ¹ represents a hydrogen atom, an OH group or an alkyl group having 1 to 12 carbon atoms.

(In the formula, R ¹⁶ represents a hydrogen atom, an alkyl group having 1 to 18 carbon atoms or an alkoxy group having 1 to 18 carbon atoms, and R ¹⁷ and R ¹⁸ represent hydrogen atoms, halogen atoms and carbon atoms independently of each other. Represents an alkyl group of 1 to 18, an alkoxy group of 1 to 18 carbon atoms, or an alkyl group of 1 to 18 carbon atoms or a phenyl group which may be substituted with a halogen atom, and R ¹⁹ is an alkyl having 1 to 18 carbon atoms. A group is represented, X ⁵ is a hydrogen atom or a methyl group, and V ² is a hydrogen atom, an OH group or an alkyl group having 1 to 12 carbon atoms.)

In the present invention, the ultraviolet absorber residue is a residue of the ultraviolet absorber and has an ultraviolet absorbing performance. For example, the triazine-based ultraviolet absorber residue has a part of the terminal of the triazine compound missing and is bound to the acrylic copolymer, so that the residue and the triazine compound have different molecular weights. However, since the weight of the missing material is small as compared to the whole, the weight of the residue and the weight of the triazine compound are considered to be the same in the present invention for convenience.

The content of the (A-4) unit of the acrylic copolymer is 0 to 15 mol%, more preferably 0.1 to 15 mol%, still more preferably 1 to 10 mol%. Above the lower limit, excellent weather resistance can be achieved, which is preferable. Further, below the upper limit, high transparency can be realized, which is preferable.

((A-5) unit)
In the case of a copolymer, it is also preferable to further contain a repeating unit represented by the following formula (A-5). By containing the (A-5) unit, a radical scavenging ability can be imparted and weather resistance can be improved.

(In the formula, R ¹⁰ represents a hydrogen atom, an alkyl group or an alkoxy group having 1 to 14 carbon atoms. Specifically, R ¹⁰ is an alkyl group or an alkoxy group having 1 to 8 carbon atoms. Examples thereof include a methyl group, an ethyl group, a propyl group, a butyl group, a methoxy group, an ethoxy group, a propoxy group, and a butoxy group.)

The content ratio of the (A-5) unit is preferably 0.1 to 15 mol%, more preferably 0.1 to 10 mol%, still more preferably 1 to 1 to 100 mol% of all the repeating units of the acrylic copolymer. It is 8 mol%.

(Other repeating units)
When the copolymer is used, it may contain other repeating units for the purpose of improving adhesiveness, weather resistance, heat resistance, and imparting functionality and the like. The other repeating unit is 30 mol% or less, preferably 20 mol% or less, and particularly preferably 10 mol% or less, based on 100 mol% of all the repeating units of the acrylic copolymer. Other repeating units can be introduced by copolymerizing a vinyl-based monomer copolymerizable with an acrylate or methacrylate monomer.

The molecular weight of the acrylic copolymer (component A) is preferably in the range of 20,000 to 10 million in terms of weight average molecular weight, more preferably 50,000 to 10 million, still more preferably 50,000 to 1 million, and most preferably. Is 50,000 to 500,000. Acrylic copolymers having such a molecular weight range are preferable because they sufficiently exhibit performance such as adhesion and strength as a primer layer (P layer) existing between the base material layer and the siloxane resin layer (T layer).

<Blocked polyisocyanate compound (B component)>
The blocked polyisocyanate compound of the component B is a compound in which a blocking agent is reacted with an isocyanate group to almost eliminate free isocyanate groups to make the compound non-reactive, and the blocking agent is separated by heating. It means a compound that becomes an isocyanate group and becomes reactive.

For example, the isocyanate group of a polyisocyanate compound includes oximes such as acetoxime and methylethylketooxime, active methylene compounds such as dimethyl malonate, diethyl malonate, acetoacetate mel, ethyl acetoacetate and acetylacetone, methanol, ethanol and 2-propanol. Examples thereof include a blocked isocyanate compound obtained by adding a blocking agent typified by alcohols such as n-butanol, sec-butanol and 2-ethyl-1-hexanol, and phenols such as phenol, cresol and ethylphenol.

Examples of the polyisocyanate compound to which a blocking agent is added include polyisocyanates, adducts of polyisocyanates and polyhydric alcohols, cyclized polymers of polyisocyanates, and isocyanate burettes.

Examples of the polyisocyanate include tolylene diisocyanate, 4,4-diphenylmethane diisocyanate, 1,5-naphthalenediocyanate, triphenylmethane triisocyanate, trizine diisocyanate, xylene diisocyanate, lysine diisocyanate, trimethylhexamethylene diisocyanate, dimerate diisocyanate, and hexamethylene diisocyanate. , Dicyclohexylmethane diisocyanate, isophorone diisocyanate and the like.

Since the isocyanate group is generated for the first time in the thermal curing reaction of the blocked isocyanate, the storage stability of the coating composition (acrylic resin composition) is excellent, and the isocyanate group is less consumed in the side reaction, which affects the coating environment. It is possible to obtain a cured film having stable coating property properties that is difficult to receive. This blocked isocyanate can be used alone or in combination of two or more.

Among the blocked isocyanates, blocked aliphatic and / or alicyclic polyisocyanate compounds are particularly preferable because of their excellent weather resistance. As the blocked aliphatic and / or alicyclic polyisocyanate compound, an adduct type obtained by reacting a hydroxy compound having 2 to 4 hydroxy groups with an alicyclic and / or alicyclic diisocyanate compound. In particular, adduct-type polyisocyanate compounds in which polyisocyanate compounds are blocked with a blocking agent, and isocyanurate-type polyisocyanate compounds in which isocyanurate-type polyisocyanate compounds are blocked with a blocking agent, which are derived from aliphatic and / or alicyclic diisocyanate compounds. It is preferably used. Among them, the aliphatic diisocyanate compound and / or the alicyclic diisocyanate compound preferably has 4 to 20 carbon atoms, and more preferably 4 to 15 carbon atoms. By setting the carbon number of the isocyanate compound in such a range, a coating film having excellent durability is formed.

Further, in the blocked polyisocyanate compound, the content ratio of the blocked isocyanate group which can become an isocyanate group by separating the blocking agent by heating is 5.5 to 50% by weight, preferably 6 in terms of isocyanate group. It is 0.0 to 40% by weight, most preferably 6.5 to 30% by weight. When the content ratio of the isocyanate group is less than 5.5% by weight, the blending amount of the blocked polyisocyanate compound with respect to the acrylic resin becomes large, and the adhesion to the base material layer becomes poor. If the isocyanate group content is more than 50% by weight, the flexibility of the coating film layer decreases, cracks occur in the coating film layer containing the siloxane resin composition when the siloxane resin layer is thermally cured, and the environment changes. It is not preferable because it may impair the durability against. The content ratio (% by weight) of the isocyanate group is determined by a method of converting the isocyanate group into urea with a known amount of amine and titrating the excess amine with an acid.

It is considered that the blocked polyisocyanate compound is desorbed from the blocking agent by heating and becomes an isocyanate group, and this isocyanate group reacts with the hydroxy group in the acrylic copolymer (crosslinking reaction).

The mixing amount ratio of the acrylic copolymer having a hydroxy group of the A component and the blocked polyisocyanate compound of the B component is the heating of the B component with respect to 1 equivalent of the hydroxy group of the acrylic copolymer of the A component. The amount of blocked isocyanate groups that can be separated into isocyanate groups is 0.8 to 1.5 equivalents, preferably 0.8 to 1.3 equivalents, and most preferably 0.9 to 1.2 equivalents. It is mixed so as to be. By preparing such a composition, the layer made of such an acrylic copolymer can maintain good adhesion to the base material layer and the siloxane resin layer, and also has a high level of cross-linking density, so that it can be exposed to ultraviolet rays or the like. It is unlikely to cause a decrease in the crosslink density due to water and oxygen, and can maintain long-term adhesion, environmental changes and durability in a high temperature environment, and is excellent in weather resistance.

If the number of isocyanate groups is less than 0.8 equivalent, the cross-linking becomes insufficient, so that the durability in a high temperature environment becomes insufficient, and the unreacted hydroxy groups show high affinity with water molecules, so that the coating layer is formed. However, it absorbs moisture, which deteriorates weather resistance and heat resistance. When the number of isocyanate groups is more than 1.5 equivalents, the coating film layer has a very high crosslink density with an allophanate bond, becomes a hard and brittle layer, and has poor followability to changes in the environment, resulting in adhesion to changes in the environment. Inferior and unfavorable.

<Curing catalyst (C component)>
In the present invention, in order to promote the dissociation of the blocking agent of the blocked polyisocyanate compound of the component B and the urethanization reaction between the regenerated isocyanate group and the hydroxy group of the acrylic copolymer of the component A, the curing of the component C is performed. A catalyst is used. Examples of the curing catalyst include organic tin compounds, quaternary ammonium salt compounds, tertiary amine compounds, organic titanium compounds, organic zirconium compounds and the like, and these compounds are used alone or in admixture of two or more. Among these curing catalysts, an organic tin compound is preferably used, and in particular, an organic tin compound represented by the following formula is preferably used.

Here, R ²⁰ is a hydrocarbon group having 1 to 8 carbon atoms, preferably an alkyl group having 1 to 8 carbon atoms, and more preferably an alkyl group having 4 to 8 carbon atoms. R ²¹ is a substituted or unsubstituted hydrocarbon group having 1 to 17 carbon atoms, preferably a substituted or unsubstituted alkyl group having 1 to 17 carbon atoms. As the substituent, an alkyl group having 1 to 4 carbon atoms is preferable. m is an integer of 0 to 3.

Typical examples of such organic tin compounds are monobutyltintris (2-ethylhexanoate), dimethyltindineodecanoate, dibutyltinbis (2-ethylhexanoate), and monobutyltintris (2-ethylhexanoate). n-Butyl Propionate), Dibutyltin Dilaurate, Monohexyltin Trioctate, Dihexyltin Dioctate, Trihexyltin Monooctate, Monohexyltin Tris (Methylmaleate), Dioctyltin Diacetate, Trioctyltin Monoacetate , Dioctyltinbis (methylmaleate), monooctyltintris (methylpropionate), dioctyltin dipropionate), trioctyltin monopropionate, monooctyltin trioctate, dioctyltin dioctate, trioctyl Examples include chinmonooctate. These compounds may be used alone or in admixture of two or more.

Typical examples of the quaternary ammonium salt compound are 2-hydroxyethyl / tri-n-butylammonium / 2,2-dimethylpropionate and 2-hydroxyethyl / tri-n-butylammonium / 2,2-dimethylbutano. Examples thereof include ate, 2-hydroxypropyltri n-butylammonium 2,2-dimethylpropionate, 2-hydroxypropyltri n-butylammonium 2,2-dimethylbutanoate and the like. Examples of the tertiary amines include dimethylethanolamine, triethylenediamine and the like.

Typical examples of the organic titanium compound include an alkoxytitanium compound such as tetraisopropyl titanate, tetrabutoxytitanate, and tetraoctyl titanate, and a titanium chelate compound such as titanium acetylacetonate and titanium ethylacetoacetate.

Typical examples of organic zirconium compounds include alkoxyzirconium compounds such as tetraisopropoxyzirconium, tetrabutoxyzirconium, and tetraoctoxyzirconium, and zirconium such as zirconium tetraacetylacetonate, zirconiumtetraethylacetoacetate, and zirconium tributoxyacetylacetonate. Examples include chelated compounds.

These quaternary ammonium salt compounds, tertiary amine compounds, organic titanium compounds, and organic zirconium compounds are used alone or in combination of two or more thereof in combination with the above organic tin compounds.

The curing catalyst of component C is used in the range of 0.001 to 0.4 parts by weight, preferably 0.002 to 0.3 parts by weight, based on 100 parts by weight of the total of components A and B. If the amount of the curing catalyst is less than 0.001 part by weight, the effect of promoting the crosslinking reaction cannot be obtained, and if it exceeds 0.4 parts by weight, the adhesion between the acrylic resin layer and the siloxane resin layer is lowered, which is not preferable.

<Amino acid silane coupling agent (D component)>
The silane coupling agent used in the present invention needs to be an amine-based silane coupling agent. When an amine-based silane coupling agent is used among various silane coupling agents, excellent weather resistance can be realized when a predetermined amount of metal oxide is contained in the siloxane resin layer (T layer). The reason is not clear, but it is presumed as follows.

In the due cycle weather resistance test, which is aimed at improvement in the present invention, deterioration due to ultraviolet rays and deterioration that occurs even in the absence of ultraviolet rays such as moisture occur at the same time, and the deterioration progresses.

Of these, deterioration caused by ultraviolet rays can be stopped by using an ultraviolet absorber such as titanium oxide, but deterioration such as the influence of moisture is extremely difficult to suppress only by blocking ultraviolet rays. In a situation where deterioration due to ultraviolet rays cannot be completely suppressed, suppression of deterioration due to moisture is not a major problem because this effect is large, but in order to achieve the extremely high weather resistance of the present application, deterioration due to moisture is also possible. A highly durable agent is needed.

When an amine-based silane coupling agent is used for the primer layer (cured layer of the acrylic resin composition) which is the base layer of the siloxane resin layer (T layer), it becomes an alkoxysilane hydrolysis condensate of the siloxane resin layer (T layer). Since the amine-based silane coupling agent in the acrylic resin layer (primer layer) forms a very strong bond, it interferes with the action of water on the primer / T layer interface, and the deterioration of this interface due to the influence of water It is thought that can be suppressed.

On the other hand, since amine-based silane coupling agents have extremely high reactivity, they act together with water to decompose the primer layer and base material layer, which are organic resins. Therefore, if the amount of amine-based silane coupling agent exceeds a predetermined amount, Weather resistance is reduced.

Among the amine-based silane coupling agents, the preferred form is represented by the following formula (1).

(In the formula, R ¹ and R ² independently refer to a methyl group and an ethyl group, respectively, and R ³ and R ⁴ independently refer to a hydrogen, a methyl group, an ethyl group, a phenyl group, (CH2) _w OH, (CH2) _x . SH (CH2) _y NH2, (C2H4NH) _z H, m refers to either 1, 2, or 3, n, w, x, y independently refer to integers of 2 to 6, and z refers to 1 to 4. Refers to the integer of.)

That is, it is an organic silicon compound having an unsubstituted or alkyl-substituted amino group linked with a group that produces a silanol group by hydrolysis and an organic group having 2 or more carbon atoms, or the organic silicon compound is hydrolyzed in a water-containing solvent. This is a hydrolyzed partial condensate solution of an organic silicon compound that produces and partially condenses silanol groups.

In the amino-based silane coupling agent, unlike other silane coupling agents, the amino group protects the condensation reaction of the silanol group generated by the hydrolysis reaction, so that the condensation reaction of the silanol group does not proceed excessively. do not have.
Therefore, a hydrolyzed partial condensate solution of an organosilicon compound can be particularly preferably used.

It is preferable that n and m in the above formula (1) satisfy n + m = 4 and 0 <n <4, and n is 2 or more and 3 or less.

Examples of the amino-based silane coupling agent represented by the above formula (1) include an alkoxy group such as a methoxy group, an ethoxy group and an isopropoxy group, an aryloxy group, an acetoxy group, an amino group or a halogen atom in a silicon atom. Examples thereof include a bonded compound, and among these, a compound in which an alkoxy group is bonded to a silicon atom, that is, an organoalkoxysilane and a solution of a partially hydrolyzed condensate thereof are particularly preferable.

Specific examples of the amino-based silane coupling agent represented by the above formula (1) include N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane and N-2- (aminoethyl) -3-. Aminopropyltrimethoxysilane, N-2- (aminoethyl) -8-aminooctyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-amino Examples thereof include propylmethyldiethoxysilane, 3-aminopropylmethyldimethoxysilane, N-methyl-3-aminopropyltrimethoxysilane, N-methyl-3-aminopropyltriethoxysilane and hydrolyzed partial condensate solutions of these compounds. .. Hydrolyzed partial condensate solutions of organosilicon compounds containing these compounds are also commercially available, and examples thereof include APZ-6601 and APZ-6633 manufactured by Toray Dow Corning and X-12-972F manufactured by Shin-Etsu Chemical Co., Ltd. Can be preferably used.

The amine-based silane coupling agent of the D component is contained in an amount of 0.1 to 10 parts by weight based on 100 parts by weight of the total of the A component and the B component. The lower limit is preferably 0.3 parts by weight or more, more preferably 1.0 part by weight or more, and 1.5 parts by weight or more with respect to 100 parts by weight of the total of the A component and the B component. This is preferable because excellent weather resistance can be obtained. On the other hand, the upper limit is preferably 7.0 parts by weight or less, more preferably 5.0 parts by weight or less, and 3.0 parts by weight or less with respect to 100 parts by weight of the total of the A component and the B component. Is preferable because excellent weather resistance can be obtained.

<Triazine-based UV absorber (H component)>
Regarding the acrylic resin composition, the following formula (H) of 0 to 40 parts by weight with respect to a total of 100 parts by weight of the A component and the B component.

(In the formula, R ⁴ is an alkyl group having 1 to 18 carbon atoms, a substituent represented by —CH ₂ CH (OH) CH _2OR ^{8 (where R 8 is} an alkyl group having 1 to 18 carbon atoms) or -CH (CH ₃ ) C (O) represents a substituent represented by O-R ⁹ (R ⁹ is an alkyl group having 1 to 18 carbon atoms), R ⁵ is a hydrogen atom and an alkyl group having 1 to 18 carbon atoms. Alternatively, it represents an alkoxy group having 1 to 18 carbon atoms, and R ⁶ and R ⁷ independently represent a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, an alkoxy group having 1 to 18 carbon atoms, or an alkoxy group having 1 to 18 carbon atoms. It represents a phenyl group which may be substituted with an alkyl group or a halogen atom, and V represents a hydrogen atom, an OH group or an alkyl group having 1 to 12 carbon atoms.
It contains a triazine-based ultraviolet absorber (H component) represented by the above formula (A), and the total content of the triazine-based ultraviolet absorber residue in the formula (A) and the H component is 1 to 40 parts by weight. It is preferably 3 to 20 parts by weight, more preferably 3 to 20 parts by weight. The H component is preferably contained in an amount of 1 to 20 parts by weight, more preferably 3 to 15 parts by weight, based on 100 parts by weight of the total of the A component and the B component.

Specifically, as the triazine-based ultraviolet absorber represented by the formula (H), ^tinubin 1577 manufactured by BASF Co., Ltd. ( ^R4 is a hexyl group, R5, R6, ^R7 and Z are hydrogen atoms) ^tinubin . 400 (R ⁴ is -CH ₂ CH (OH) CH ₂ O-R ⁸ (R ⁸ is dodecyl group and tridecyl group), R ⁵ , R ⁶ , R ⁷ and Z are hydrogen atoms) Chinubin 405 (R ⁴ is- CH ₂ CH (OH) CH ₂ O-R ⁸ (R ⁸ is an octyl group), R ⁵ , R ⁶ , R ⁷ and Z are methyl groups) Tinubin 460 (R ⁴ is a butyl group, R ⁵ , R ⁶ , R) ⁷ is a butyloxy group, Z is an OH group) Tinubin 479 ( ^R4 is -CH (CH ₃ ) C (O) OR ⁹ (R ⁹ is an octyl group) R ⁵ is a hydrogen atom, R ⁶ and R ⁷ are phenyl Group, Z is a hydrogen atom) and the like.

The triazine-based ultraviolet absorber represented by the formula (H) may be used alone or in combination of two or more.

<Light stabilizer>
In the present invention, the acrylic resin composition containing the components A to D can further contain a light stabilizer. Examples of the light stabilizer include bis (2,2,6,6-tetramethyl-4-piperidyl) carbonate, bis (2,2,6,6-tetramethyl-4-piperidyl) succinate, and bis (2,2). , 6,6-Tetramethyl-4-piperidyl) sevacate, 4-benzoyloxy-2,2,6,6-tetramethylpiperidine, 4-octanoyloxy-2,2,6,6-tetramethylpiperidine, bis (2,2,6,6-tetramethyl-4-piperidyl) Diphenylmethane-p, p'-dicarbamate, bis (2,2,6,6-tetramethyl-4-piperidyl) benzene-1,3-di Hindered amines such as sulfonate, bis (2,2,6,6-tetramethyl-4-piperidyl) phenylphosphite, nickel bis (octylphenylsulfide, nickel complexx-3,5-di-t-butyl-4-hydroxy) Examples thereof include nickel complexes such as benzyl phosphate monoethylate and nickel dityldithiocarbamate. These photostabilizers may be used alone or in combination of two or more, in a total of 100 parts by weight of the component (A) and the component (B). On the other hand, it is preferably used in an amount of 0.01 to 50 parts by weight, more preferably 0.05 to 10 parts by weight.

<About the film thickness of the acrylic resin layer>
The film thickness of the layer made of the acrylic resin composition for coating containing the components A to D is preferably 1 to 15 μm, more preferably 2 to 10 μm.

If the film thickness is less than 1 μm, the transmittance of ultraviolet rays becomes high, yellowing of the base material layer occurs, and the adhesion between the base material layer and the acrylic resin layer is lowered, so that the weather resistance may be lowered. .. If the film thickness exceeds 15 μm, the durability in a high temperature environment tends to decrease because the internal stress increases and the crosslinking reaction does not proceed sufficiently during thermosetting. In addition, the solvent used to dissolve the acrylic resin composition for coating containing the components (A) to (D), which will be described later, tends to be insufficiently volatilized, and the solvent remains in the coating film, resulting in heat resistance and water resistance. And may impair weather resistance.

<About the method of forming the acrylic resin layer>
In the present invention, as a method of forming an acrylic resin layer (P layer), the acrylic resin composition containing components A to D is dissolved in a volatile solvent to obtain an acrylic resin paint for coating, and this paint is used. Examples thereof include a method of applying to at least one surface of the base material layer and then removing the solvent by heating or the like. After removing the solvent, further heating causes a cross-linking reaction between the hydroxy group in the acrylic resin composition and the generated isocyanate group to form an acrylic resin layer.

It is necessary that such a solvent does not react with the base material or dissolve the base material. Examples of such a solvent include ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone, ethers such as tetrahydrofuran, 1,4-dioxane and 1,2-dimethoxyethane, and esters such as ethyl acetate and ethoxyethyl acetate. , Methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, 2-methyl-1-propanol, 2-methyl-2-propanol, 2-ethoxyethanol, 1-methoxy-2-propanol, Examples thereof include alcohols such as 2-butoxyethanol, hydrocarbons such as n-hexane, n-heptane, isooctane, benzene, toluene, xylene, gasoline, light oil and kerosene, acetonitrile, nitromethane, water and the like, and these are used alone. It may be used, or two or more kinds may be mixed and used.

In the acrylic resin coating material for coating, the concentration of the acrylic resin composition (solid form) containing the components A to D is preferably 1 to 50% by weight, more preferably 3 to 30% by weight.

The acrylic resin paint for coating is applied to the base material layer by a method such as a bar coating method, a dip coating method, a flow coating method, a spray coating method, a spin coating method, a roller coating method, etc., and the shape of the base material layer to be coated. It can be appropriately selected according to the above. The member coated with the acrylic resin paint is usually dried and removed from the solvent at a temperature equal to or lower than the heat distortion temperature of the base material layer from room temperature, and becomes an acrylic resin layer (P layer) by heat curing.

It is preferable that such heat curing is performed at a high temperature within a range where there is no problem in the heat resistance of the base material layer, because the curing can be completed more quickly. At room temperature, thermal curing does not proceed completely, and a cured layer (acrylic resin layer) having a sufficient crosslink density required for the first layer cannot be obtained. In the process of thermosetting, the crosslinkable groups in the acrylic resin composition react to increase the crosslink density of the cured layer, resulting in a cured layer having excellent adhesion, heat resistance and water resistance, and durability in a high temperature environment.

The thermosetting is preferably in the range of 80 to 160 ° C, more preferably in the range of 100 to 140 ° C, most preferably in the range of 110 to 130 ° C, preferably in the range of 10 minutes to 3 hours, more preferably in the range of 20 minutes to 2 hours. By cross-linking the crosslinkable group, a transparent plastic base material (member) in which the acrylic resin layer is laminated as the first layer on the base material layer can be obtained. If the thermosetting time is shorter than 10 minutes, the crosslinking reaction may not proceed sufficiently, resulting in a coating film layer (acrylic resin layer) having poor durability and weather resistance in a high temperature environment. Further, in terms of the performance of the coating film, a thermosetting time of 3 hours or less is sufficient.

By thermosetting the acrylic resin composition to form an acrylic resin layer (P layer), the adhesion between the siloxane resin layer (T layer) and the base material layer is improved, and the wear resistance and weather resistance are excellent. Acrylic laminate can be obtained.

<Organosiloxane resin composition>
The organosiloxane resin composition contains colloidal silica (component E), alkoxysilane hydrolyzed condensate (component F) and metal oxide (component G).

<Coloidal silica (E component)>
As the colloidal silica of the E component, silica fine particles having a diameter of 5 to 200 nm, more preferably a diameter of 5 to 40 nm are colloidally dispersed in water or an organic solvent.

As such colloidal silica, specifically, as a product dispersed in an acidic aqueous solution, Snowtex O of Nissan Chemical Industry Co., Ltd., Cataloid SN30 of Catalytic Chemical Industry Co., Ltd., as a product dispersed in a basic aqueous solution. Snowtex 30 and Snowtex 40 from Nissan Chemical Industry Co., Ltd., Cataloid S30 and Cataloid S40 from Catalytic Chemical Industry Co., Ltd., and MA-ST and IPA-ST from Nissan Chemical Industry Co., Ltd. as products dispersed in organic solvents. , NBA-ST, IBA-ST, EG-ST, XBA-ST, NPC-ST, DMAC-ST and the like.

The colloidal silica can be used in either an aqueous dispersion type or an organic solvent dispersion type, but it is preferable to use an aqueous dispersion type. In the case of water-dispersed colloidal silica, a large number of hydroxyl groups are present on the surface of the silica fine particles, and these are strongly bonded to the alkoxysilane hydrolyzed condensate, so that a plastic molded body having better wear resistance can be obtained. Conceivable. The water-dispersed colloidal silica can be used in either an acidic aqueous solution dispersion type or a basic aqueous solution dispersion type, but is acidic from the viewpoints of versatility in selection of curing catalyst, appropriate hydrolysis of trialkoxysilane, and realization of condensed state. Aqueous solution-dispersed colloidal silica is preferably used.

<Hydrolytic condensate of alkoxysilane (F component)>
The hydrolysis condensate (F component) of alkoxysilane used in the present invention is obtained by hydrolyzing and condensing the alkoxysilane of the following formula (F).

(However, R ¹ and R ² in the formula are one or more selected from the group consisting of an alkyl group having 1 to 4 carbon atoms, a vinyl group, or a methacryloxy group, an amino group, a glycidoxy group and a 3,4-epoxycyclohexyl group, respectively. It is an alkyl group having 1 to 3 carbon atoms substituted with a group, R ³ is an alkyl group having 1 to 4 carbon atoms, m and n are integers of 0, 1 and 2, respectively, and m + n is 0. It is an integer of 1 or 2, and m + n is preferably an integer of 0 or 1.)

Specific examples of the alkoxysilane include tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, tetraisopropoxysilane, tetra-n-butoxysilane, tetraisobutoxysilane, and methyltrimethoxysilane. Methyltriethoxysilane, ethyltrimethoxysilane, isobutyltrimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, γ-methacryloxypropyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, γ -Glysidoxypropyltrimethoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, N-β (aminoethyl) -γ-aminopropyltrimethoxysilane, N-β (aminoethyl) -γ -Aminopropyltriethoxysilane, dimethyldimethoxysilane, vinylmethyldimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-aminopropylmethyldiethoxysilane, etc., among others. Alkyltrialkoxysilanes are preferred, especially methyltrimethoxysilanes and methyltriethoxysilanes. These can be used alone or in admixture. Further, in order to impart flexibility to the cured film depending on the application, it is also preferable to mix and use a bifunctional alkoxysilane such as dimethyldimethoxysilane.

Further, in order to obtain a coating composition for forming a siloxane resin layer (T layer) having particularly excellent wear resistance, 70% by mass to 100% by mass of the alkoxysilane in terms of solid content is methyltrialkoxysilane. It is preferable to have.

The F component is a mixture of a part or all of the alkoxysilane hydrolyzed and a condensate in which part or all of the hydrolyzate is condensed, and these are obtained by subjecting the sol-gel reaction. Is.

In the present invention, the mixing ratio of the E component and the F component in the organosiloxane resin composition is the stability of the organosiloxane resin composition, the abrasion resistance, the scratch resistance, the adhesion and the crack of the obtained cured layer (T layer). When the total of the E component and the F component is 100% by weight, the mixing ratio of the two components is 10 to 60% by weight for the E component and R ₁₀ mR ₁₁ nSiO _for the F component. Converted to _{4-mn) / 2} , it is 40 to 90% by weight, preferably the E component is converted to 10 to 40% by weight, and the F component is converted to R ₄ mR ₅ nSiO _{(4-mn) / 2} . It is 60 to 90% by weight.

The organosiloxane resin composition containing the E component and the F component can be adjusted by performing an alkoxysilane hydrolysis condensation reaction.

When an aqueous dispersion type colloidal silica dispersion is used, the water required for the hydrolysis reaction of alkoxysilane is supplied from this dispersion, and water may be further added if necessary. Usually 1 to 10 equivalents, preferably 1.5 to 7 equivalents of water is used with respect to 1 equivalent of alkoxysilane.

The hydrolysis condensation reaction of alkoxysilane needs to be carried out under acidic conditions, and an acid is generally used as a hydrolyzing agent in order to carry out the hydrolysis under such conditions. Such an acid may be added to the alkoxysilane or colloidal silica dispersion in advance, or both may be added after mixing. Further, the addition can be divided into one time or two or more times. Examples of such acids include inorganic acids such as hydrochloric acid, sulfuric acid, nitrate, phosphoric acid, nitrite, perchloric acid and sulfamic acid, formic acid, acetic acid, propionic acid, butyric acid, oxalic acid, succinic acid, maleic acid, lactic acid and paratoluene sulfone. Organic acids such as formic acid, acetic acid, propionic acid, butyric acid, oxalic acid, succinic acid, maleic acid and the like are preferable, and acetic acid is particularly preferable.

When an inorganic acid is used as such an acid, it is usually used at a concentration of 0.0001 to 2, preferably 0.001 to 0.1, and when an organic acid is used, it is usually used with respect to 100 parts by weight of alkoxysilane. It is used in the range of 0.1 to 50 parts by weight, preferably 1 to 30 parts by weight.

The conditions for hydrolysis and condensation reaction of alkoxysilane vary depending on the type of alkoxysilane used, the type and amount of colloidal silica coexisting in the system, so it cannot be said unconditionally, but the temperature of the system is usually 20 to 70 ° C. The reaction time is from 1 hour to several days. According to the above method, a siloxane resin layer having no precipitation and having more excellent wear resistance can be obtained.

<Metal oxide (G component)>
The G component used in the present invention is a metal oxide having an action of absorbing ultraviolet rays, and at least one metal oxide selected from the group consisting of titanium oxide, zinc oxide, cerium oxide, tin oxide, and tungsten oxide is a metal oxide. It is preferably used because it is less decomposed by light.

The G component of the present invention may be surface-coated.

Metal oxides that have the effect of absorbing ultraviolet rays have a photocatalytic effect when releasing the absorbed ultraviolet energy, but for various purposes such as suppressing the influence of this effect and improving the dispersibility in paints. Depending on the case, the surface may be treated with a covering material before use.

The coating material includes organic, inorganic, and inorganic materials, and is classified into silicon oxide-based resin, aluminum oxide-based resin, and other metal oxide-based resins in terms of the type of metal oxide used.

Further, it is classified into a dry type and a wet type according to the difference in the treatment method.
In particular, as the G component used in the present invention, metal oxide fine particles surface-treated with a coating material so that the amount of hydroxyl groups on the surface thereof is measured by an infrared absorption method and becomes 3.5 to 5 / nm ² is preferably used. To.

The type of dressing and the treatment method are selected according to the purpose. In the present invention, the surface treatment method is not particularly limited, but a metal oxide surface-coated with a silicon oxide-based compound is preferably used in order to realize a hydroxyl group amount of 3.5 to 5 / nm ² on the surface of the metal oxide. To. Further, a wet treatment method is more preferably used.

The metal oxide fine particles mainly pass through the hydroxyl groups on the surface to realize the affinity with the resin component of the organosiloxane resin composition which is the coating material, and the amount of the hydroxyl groups on the surface is 3.5 to 5 / nm ² . Therefore, an appropriate affinity between the coating resin and the metal oxide fine particles is realized. As a result, it shows very excellent weather resistance because the fine particles do not fall off in the weather resistance test. Moreover, a very dense coat layer is formed to help the organosiloxane resin to have an appropriate arrangement when the organosiloxane resin composition is cured. As a result, it exhibits excellent wear resistance. Furthermore, in order to help the organosiloxane resin to have an appropriate arrangement during curing, the adhesion of the coat layer interface is also improved, and as a result, excellent weather resistance is obtained especially in the weather resistance test considering the influence of the dew cycle. Can be shown.

Further, the G component used in the present invention has D90 of 100 nm or less and D90 / D50 when the cumulative 50% particle size and the cumulative 90% particle size in the laser diffraction method particle size distribution measurement are D50 and D90, respectively. It is preferably 20 or less.

When D90 is not more than the upper limit, it is preferable because it becomes a cured layer having excellent transparency with less aggregation in the process of forming the thermosetting film. The upper limit of D90 is more preferably 80 nm or less. Further, the lower limit of D90 may be any particle size of the primary particles in which the metal oxide is not aggregated, and D90 is preferably 10 nm or more. On the other hand, D90 / D50 is a guideline for the uniformity of the particle size, and when D90 / D50 is not more than the upper limit, the uniformity of the particle size is excellent, so that the storage stability of the coating composition and the long-term storage stability of the cured layer (T layer) are obtained. Durability is good. The upper limit of D90 / D50 is more preferably 10 or less, further preferably 5 or less. Further, the lower limit of D90 / D50 is preferably 1.0.

Here, the particle size and the particle size distribution of the fine particles of the metal oxide are measured using a laser diffraction type particle size distribution measuring device (Microtrac UPA-ST150 manufactured by Nikkiso Co., Ltd.). The particle size distribution measuring device measures fine particles of a metal oxide having a particle size range of 3 to 6000 nm. Further, the particle size distribution is obtained by the volume distribution, and the numerical values of the particle sizes D50 and D90 corresponding to the cumulative 50% and the cumulative 90% from the fine particle side are obtained. The ratio of D90 / D50 is calculated based on these numerical values.

The content of the G component is 8 to 60 parts by weight with respect to 100 parts by weight of the total of the E component and the F component. The lower limit is preferably 10 parts by weight, more preferably 13 parts by weight, based on 100 parts by weight of the total of the E component and the F component. The upper limit is preferably 50 parts by weight, more preferably 45 parts by weight, and even more preferably 40 parts by weight with respect to 100 parts by weight of the total of the E component and the F component.

Further, the ratio of the content of the D component to the total 100 parts by weight of the A component and the B component and the content of the G component to the total 100 parts by weight of the E component and the F component is 15 to 200. It is preferably 30 to 150, and more preferably 30 to 150. In this range, good adhesion can be obtained between the acrylic resin layer and the siloxane resin layer, which is preferable.
The reason is not clear, but in addition to the van der Waals force acting strongly due to the close proximity of the conversion solubility parameters of both layers, the aminosilane coupling agent in the acrylic resin layer and the siloxane hydroxyl group in the siloxane resin layer It is presumed that good adhesion is achieved by causing a condensation reaction to form a covalent bond.

<Curing catalyst (I component)>
The organosiloxane resin composition used in the present invention preferably further contains a curing catalyst. Examples of the curing catalyst include lithium salts of aliphatic carboxylic acids such as formic acid, acetic acid, propionic acid, butyric acid, lactic acid, tartaric acid and succinic acid, alkali metal salts such as sodium salt and potassium salt, benzyltrimethylammonium salt and choline salt. , Tetramethylammonium salt, tetraethylammonium salt and other quaternary ammonium salts, and specifically, sodium acetate, potassium acetate, choline acetate and benzyltrimethylammonium acetate are preferably used. The curing catalyst is preferably used in the range of 0.01 to 10 parts by weight, more preferably 0.1 to 5 parts by weight, based on 100 parts by weight of the total of the E component and the F component.

<About the method of forming the siloxane resin layer>
As a method for forming a cured layer (T layer) of a siloxane resin using an organosiloxane resin composition, an organosiloxane resin composition containing an E component, an F component and a G component is dissolved in a solvent for coating. The organosiloxane resin coating material (coating composition) is formed by applying the coating organosiloxane resin coating material onto the P layer formed on the substrate and then heat-curing the coating material.

As such a solvent, it is necessary that the organosiloxane resin composition is stably dissolved, and for that purpose, it is desirable to use a solvent in which at least 20% by weight or more, preferably 50% by weight or more is alcohol.

Specific examples of such alcohols include methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, 2-methyl-1-propanol, 2-ethoxyethanol and 4-methyl-2-pentanol. , 2-Butoxyethanol and the like, and among them, low boiling alcohol having 1 to 4 carbon atoms is preferable, and 2-propanol is particularly preferable in terms of solubility, stability and coatability.

In the solvent, water in the water-dispersed colloidal silica that does not participate in the hydrolysis reaction, a lower alcohol generated by hydrolysis of alkoxysilane, and organic solvent-dispersed colloidal silica are used. It also contains an organic solvent as a dispersion medium and an acid added for adjusting the pH of the organosiloxane resin coating material for coating (coating composition).

Acids used for pH adjustment include inorganic acids such as hydrochloric acid, sulfuric acid, nitrate, phosphoric acid, nitrite, perchloric acid and sulfamic acid, formic acid, acetic acid, propionic acid, butyric acid, oxalic acid and succinic acid. , Maleic acid, lactic acid, paratoluenesulfonic acid and other organic acids, and organic carboxylic acids such as formic acid, acetic acid, propionic acid, butyric acid, oxalic acid, succinic acid and maleic acid from the viewpoint of ease of pH control. preferable.

Other solvents that can be used are those that need to be miscible with water / alcohol, such as ketones such as acetone, methyl ethyl ketone and methyl isobutyl ketone, and ethers such as tetrahydrofuran, 1,4-dioxane and 1,2-dimethoxyethane. , Ethyl acetate, n-butyl acetate, isobutyl acetate, ethoxyethyl acetate and the like.

The amount of the solvent used is preferably 50 to 900 parts by weight, more preferably 150 to 700 parts by weight, based on 100 parts by weight of the total of the E component and the F component.

It is desirable to adjust the pH of the organosiloxane resin coating material for coating to preferably 3.0 to 6.0, more preferably 4.0 to 5.5 by adjusting the content of the acid and the curing catalyst. By adjusting the pH within this range, gelation of the organosiloxane resin paint at room temperature can be prevented and storage stability can be increased. The organosiloxane resin paint usually becomes a stable paint by further aging for several hours to several days.

It is preferable that the formation of the T layer made of the organosiloxane resin coating material for coating is continuously performed following the formation of the P layer.

As a coating method for applying the organosiloxane resin paint for coating, a method such as a bar coating method, a dip coating method, a flow coating method, a spray coating method, a spin coating method, a roller coating method, etc. is used for the base material layer to be coated. It can be appropriately selected according to the shape. The base material layer coated with the organosiloxane resin paint for coating is usually a cured film that is cured by reacting with heating after drying and removing the solvent from room temperature at a temperature equal to or lower than the heat distortion temperature of the base material layer. A hardened layer is formed. It is preferable that the thermosetting is performed at a high temperature within a range where there is no problem in the heat resistance of the base material layer because the curing can be completed faster. At room temperature, the progress of thermal curing is slow, and a cured film cannot be obtained quickly. This means that the organosiloxane resin composition in the coating organosiloxane resin coating is partially condensed. In the process of such thermal curing, the remaining Si—OH undergoes a condensation reaction to form a Si—O—Si bond, resulting in a siloxane resin layer (cured film) having excellent wear resistance.

The thermosetting temperature is preferably in the range of 50 ° C. to 200 ° C., more preferably in the range of 80 ° C. to 160 ° C., further preferably in the range of 100 ° C. to 140 ° C., and the curing time is preferably in the range of 10 minutes to 4 hours. , More preferably 20 minutes to 3 hours, still more preferably 30 minutes to 2 hours.

<About the film thickness of the siloxane resin layer>
The thickness of the siloxane resin layer (T layer) made of the organosiloxane resin composition is preferably 2 to 10 μm, more preferably 3 to 8 μm. If the thickness of the coating film layer is within the range, cracks are unlikely to occur in the T layer due to the stress generated during thermal curing, and the adhesion between the T layer and the acrylic resin layer (first layer) may decrease. It is easy to obtain a siloxane resin layer having sufficient wear resistance, which is the object of the present invention.

<Base layer>
The base material layer used in the present invention is usually in the form of a sheet or a plate. Then, as long as it is formed by molding a resin that forms a layer having high light transmittance, it may be either a thermoplastic resin or a thermosetting resin. Thermoplastic resins, especially amorphous thermoplastics, are preferred for applications where high transparency is required. Specific examples of the amorphous thermoplastic resin include polycarbonate resin, acrylic resin such as polymethylmethacrylate, polyethylene terephthalate resin, polyethylene naphthalate resin, cyclic polyolefin resin, polyphenylene ether resin, polysulfone resin, polyethersulfone resin, and polystyrene resin. , Polypropylene resin and the like. Among these, a polycarbonate resin having excellent heat resistance, impact resistance, and the like is particularly preferable when considering its use in automobile window materials, building materials, camera lenses, and solar cell surface protection plates.

Regarding the heat resistance of the resin, the heat distortion temperature (HDT) is preferably 100 ° C. or higher, more preferably 120 ° C. or higher, still more preferably 130 ° C. or higher.

The polycarbonate resin is, for example, a polycarbonate resin obtained by reacting a divalent phenol with a carbonate precursor by an interfacial polycondensation method, a melting method, or the like. Typical examples of divalent phenols are 2,2-bis (4-hydroxyphenyl) propane (commonly known as bisphenol A), 2,2-bis (3-methyl-4-hydroxyphenyl) propane, 2, 2-bis (3,5-dimethyl-4-hydroxyphenyl) propane, 1,1-bis (4-hydroxyphenyl) ethane, 1,1-bis (4-hydroxyphenyl) cyclohexane, 2,2-bis (4) -Hydroxyphenyl) butane, 2,2-bis (4-hydroxyphenyl) -3-methylbutane, 9,9-bis {(4-hydroxy-3-methyl) phenyl} fluorene, 2,2-bis (4-hydroxy) Phenyl) -3,3-dimethylbutane, 2,2-bis (4-hydroxyphenyl) -4-methylpentane, 1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane and α, Examples thereof include α'-bis (4-hydroxyphenyl) -m-diisopropylbenzene, bis (4-hydroxyphenyl) sulfate, bis (4-hydroxyphenyl) sulfone, and bisphenol A is preferable. These divalent phenols can be used alone or in admixture of two or more.

As the carbonate precursor, carbonyl halide, carbonate ester, haloformate and the like are used, and specific examples thereof include phosgene, diphenyl carbonate and dihaloformate of divalent phenol.

In producing a polycarbonate resin by reacting a dihydric phenol with a carbonate precursor by an interfacial polycondensation method or a melting method, a catalyst, a terminal terminator, a divalent phenol antioxidant, etc. are used as necessary. You may use it. Further, the polycarbonate resin may be a branched polycarbonate resin obtained by copolymerizing a trifunctional or higher polyfunctional aromatic compound, or a polyester carbonate resin obtained by copolymerizing an aromatic or aliphatic bifunctional carboxylic acid. Further, it may be a mixture of two or more of the obtained polycarbonate resins.

The molecular weight of the polycarbonate resin is preferably 10,000 to 50,000, more preferably 15,000 to 35,000 in terms of viscosity average molecular weight (M). A polycarbonate resin having such a viscosity average molecular weight is preferable because sufficient strength can be obtained and melt fluidity at the time of molding is also good.

The viscosity average molecular weight referred to in the present invention is obtained by inserting the specific viscosity (η _sp ) obtained from a solution of 0.7 g of a polycarbonate resin in 100 ml of methylene chloride at 20 ° C into the following equation.

η _sp / c = [η] +0.45 × [η] ² c (however, [η] is the ultimate viscosity)
[Η] = 1.23 × 10 ^-4 M ^0.83
c = 0.7
In addition, as the polycarbonate resin, various copolymerized polycarbonates such as a polycarbonate resin obtained by copolymerizing isosorbide and an aliphatic diol and a polycarbonate-polyorganosiloxane copolymer can also be preferably exemplified.

The thermoplastic resin constituting the preferable base material layer of the present invention may be used alone or in combination of two or more. Polycarbonate resin preferably used as a light-transmitting substrate, acrylic resin such as polymethylmethacrylate, cyclic polyolefin resin, polyphenylene ether resin and the like can be used alone or in combination of two or more. Further, a resin other than the main component resin can be blended as long as the characteristics of the present invention are not impaired.

Further, on the base material layer in the present invention, if necessary, known additives (infrared shielding material, infrared absorber, ultraviolet absorber, dye pigment, compound having heat ray absorbing ability, various stabilizers, antioxidants, etc. It may contain a mold release agent, a brewing agent, a hydrolysis improver, a flame retardant, a drip inhibitor, an antistatic agent, etc.), various fillers, and the like.

The thickness of the base material layer in the present invention is in the range of 1 to 20 mm, more preferably 2 to 10 mm, and further preferably 3 to 7 mm. When the thickness is at least the lower limit, the mechanical strength is good, which is preferable. On the other hand, when the thickness is not more than the upper limit, it is preferable because a base material layer having good surface smoothness and less optical distortion (perspective distortion, etc.) can be obtained.

Hereinafter, the present invention will be described in detail with reference to examples, but the present invention is not limited thereto as long as the gist of the present invention is not exceeded. The physical properties of Examples and Comparative Examples were evaluated according to the following method.

(I) Measurement items (1) Appearance The appearance (presence or absence of foreign matter and whitening) of the double-sided coating layer of the test piece and the presence or absence of cracks were visually confirmed.

(2) Transparency Using NDH-2000 manufactured by Nippon Denshoku, the total light transmittance and haze were measured by Method 2, A light source (JIS-K7136 compliant).

(3) Adhesion Make 100 grids with a cutter knife on one surface of the double-sided coat layer and press Nichiban adhesive tape (trade name "Cellotape (registered trademark)") to make it strong vertically. After repeating the peeling operation three times, the number of grids remaining on the substrate layer was used for evaluation.

(4) The adhesion of the coat layer after the heat-resistant water-resistant test piece was immersed in boiling water for 3 hours was evaluated.

(5) Abrasion resistance According to JIS K6735, a Taber wear test of 500 rotations was performed with a load of 500 g using a wear wheel of CS-10F (TYPE IV) manufactured by Calibrase on one surface of the double-sided coat layer, and after the Taber wear test. The difference between the haze and the haze before the Taber wear test ΔH was measured and evaluated.

(6) Weather resistance test-1 (SXOM, evaluation method described in Patent Document 1)
Using Super Xenon Weather Meter SX-75 manufactured by Suga Test Instruments Co., Ltd. with one side of the test piece as the UV irradiation surface, UV irradiation intensity 180 W / m ² , black panel temperature 63 ° C, 18 minutes out of 120 minutes under rainfall conditions. The exposure test was performed, and the test piece was taken out every 1000 hours, and the appearance and adhesion were evaluated in the same manner as in (6).
Those having a performance of 6000 hours (3900 MJ / m ² ) or more were judged to be acceptable, and those having a performance of 10000 hours or more were judged to have particularly excellent weather resistance.

(7) Weather resistance test-2 (SUV)
The test piece was irradiated with metal weather (manufactured by Daipla Wintes Co., Ltd., model: KU-R5N-W, filter type: KF-2 filter) at an illuminance of 90 mW / cm ² (63 ° C, 70% RH). A dew cycle test was conducted with 12 hours of time, dew condensation (70 ° C, 90% RH) for 4 hours and darkness (30 ° C, 98% RH) for 4 hours, and the appearance (crack) was taken out every 5 cycles. Presence / absence observation, close contact (pressing cellophane tape (registered trademark) on the substrate,
The operation of peeling strongly vertically was performed, and the presence or absence of peeling of the coat layer was observed). The dew cycle test was continued because it was judged that the one with no cracks in appearance and no peeling of the coat layer in the adhesion test maintained the performance. The above test was carried out until cracks were generated in appearance or peeling was performed in the adhesion test, and the maximum number of cycles that maintained the performance was defined as the number of performance retention cycles.
Those having a performance of 60 cycles or more were judged to be acceptable, and those having a performance of 90 cycles or more were judged to have particularly excellent weather resistance.

(II-1) Synthesis of Acrylic Copolymers (A) to (I) Solutions [Reference Example 1]
A reflux cooler and a stirrer are provided, and 79.9 parts by mass of ethyl methacrylate (hereinafter referred to as EMA), 33.6 parts by mass of cyclohexyl methacrylate (hereinafter referred to as CHMA), and 2-hydroxyethyl methacrylate (hereinafter referred to as CHMA) are contained in a nitrogen-substituted flask. 13.0 parts by mass (hereinafter referred to as HEMA), 126.6 parts by mass of methyl isobutyl ketone (hereinafter referred to as MIBK) and 63.3 parts by mass of 2-butanol (hereinafter referred to as 2-BuOH) were added and mixed. After deoxidizing the mixture by aerating nitrogen gas for 15 minutes, the temperature is raised to 70 ° C. under a nitrogen gas stream, 0.33 part by mass of azobisisobutyronitrile (hereinafter referred to as AIBN) is added, and nitrogen gas is added. The reaction was carried out in an air stream at 70 ° C. for 5 hours with stirring. Further, 0.08 part by mass of AIBN was added, the temperature was raised to 80 ° C., and the reaction was carried out for 3 hours to obtain an acrylic copolymer (A) solution having a non-volatile content concentration of 39.6% by mass. The weight average molecular weight of the acrylic copolymer (A) was 125,000 in terms of polystyrene from the measurement of GPC (column; Shodex GPCA-804, eluent; chloroform).

[Reference Examples 2-9]
Acrylic copolymer (B) to (I) solutions were obtained in the same manner as in Reference Example 1 except that the amount of each agent added was as shown in Table 1.

EMA: Ethyl methacrylate CHMA: Cyclohexyl methacrylate HEMA: 2-Hydroxyethyl methacrylate LA-82: 1,2,2,6,6-pentamethyl-4-piperidyl methacrylate MOI-T: 2-hydroxy-4- [2- (2) ′ -Methyloxyethylaminocarboxy) -3- (2'ethyl) hexyl) Oxy] Phenyl-4,6-bis (2,4-dimethoxyphenyl) -1,3,5-triazine MIBK: Methylisobutylketone 2 -BuOH: 2-butanol AIBN: azobisisobutyronitrile

(II-2) Adjustment of Acrylic Resin Paints (i-1) to (i-19) [Reference Example 10]
To 100 parts by mass of the acrylic copolymer (A) solution, 43.2 parts by mass of MIBK, 21.6 parts by mass of 2-BuOH, and 83.5 parts by mass of 1-methoxy-2-propanol were added and mixed, and tinubin 400 (BASF) was added. Triazine-based ultraviolet absorber (10.6 parts by mass), ADEKASTAB LA-52 (Hinderdamine-based light stabilizer manufactured by ADEKA Co., Ltd.) 8.4 parts by mass, and 1 equivalent of hydroxy group of acrylic polymer in acrylic resin solution. On the other hand, 10.6 parts by mass of VESTANAT B1358 / 100 (polyisocyanate compound precursor manufactured by Degusa Japan Co., Ltd.) was added so that the amount of the isocyanate group became 1.0 equivalent, and further, dimethyldineodecanoate tin (DMDNT) was added. 0.03 part by mass was added and stirred at 25 ° C. for 1 hour to prepare a composition (acrylic resin paint) (i-1) containing an acrylic resin as a main component.

[Reference Examples 11 to 28]
Acrylic resin paint (i-2) to (i-19) solutions were obtained in the same manner as in Reference Example 10 except that the amount of each agent added was as shown in Table 2.

VEST: VESTANAT B1358 / 100 (blocked polyisocyanate compound precursor)
Duranate: Blocked hexamethylene diisocyanate precursor DMDNT: Dimethyldineodecanoate tin DBTDL: Dibutyl dilaurate tin BTEHT: Butyltriethylhexanoate tin UVA-1: BASF UV absorber Tinubin 400
UVA-2: BASF's UV absorber Chinubin 405
UVA-3: BASF's UV absorber Chinubin 479
APZ6601: Silane coupling agent hydrolyzed condensate solution manufactured by Toray Dow Corning Co., Ltd. KBM-903: 3-aminopropyltrimethoxysilane KBM-403: 3-glycidoxypropyltrimethoxysilane KBM-803: 3-mercaptopropyltrimethoxy Silane HALS-1: ADEKASTAB LA-52 manufactured by ADEKA Co., Ltd.
HALS-2: ADEKASTAB LA-57 manufactured by ADEKA CORPORATION

[Synthesis Example 1 (Preparation of Metal Oxide Fine Particle Dispersion)]
(1) Production of solid titanium oxide:
200 g of 30% titanium sulfate hydrate (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) was placed in an autoclave with a volume of 500 mL (manufactured by Pressure-Resistant Glass Industry Co., Ltd., product name: TEM-D500), and this was charged at 200 ° C., 1 It was hydrothermally treated for 240 minutes under the condition of 5.5 MPa. Then, the reaction mixture in the autoclave was discharged to a container held in a water bath at 25 ° C. via a sampling tube, and the reaction was stopped by rapid cooling to obtain a titanium oxide dispersion liquid (i). ..

The obtained titanium oxide dispersion was placed in a cellophane bag and treated with running water for 3 hours to remove sulfuric acid. ) 30 g was obtained.

(2) Production of surface-coated titanium oxide dispersion:
To a separable flask equipped with a magnetic rotor and a thermometer, 30 g of the titanium oxide solid (I), 70 g of water, and 10 g of ethanol produced earlier were added, and then the separable flask was combined with μReactorEx (Shikoku Measurement Industry Co., Ltd.). It was placed in (manufactured by) and magnetically stirred while irradiating a microwave with a frequency of 2.45 GHz and an output of 1,000 W for 1 minute. Further, after adding 0.5 g of a 0.1 mol / L sodium hydroxide aqueous solution and 1.8 parts by mass of tetraethoxysilane, the magnetism is continued while irradiating with a microwave having a frequency of 2.45 GHz and an output of 1,000 W for 10 minutes. Stirred. The contents are transferred to a cellophane bag and immersed in running water for 3 hours to wash away excess ions, then taken out into a round-bottom flask and concentrated by vacuum batch distillation to obtain a surface-coated titanium oxide dispersion (G-1). Made.

(3) Method for measuring the amount of hydroxyl groups on the surface of metal oxide fine particles (G-1) 10 g was heated and dried at 80 ° C. under a reduced pressure of 500 Pa to obtain 1 g of surface-coated titanium oxide fine particle powder (G-2). 1 g of fine potassium bromide powder and 100 mg of (G-2) were mixed in a mortar, placed in a mold and compressed to prepare a 0.1 mm thick tablet for IR measurement.
The prepared tablet was set in a Fourier transform infrared spectrophotometer FT / IR-4600 manufactured by Nippon Spectroscopy Co., Ltd., and the IR spectrum was measured.
The amount of hydroxyl groups on the surface of the fine particles was specified by comparing the absorption peak of MO-H expansion and contraction vibration of 3000 to 4000 cm ^-1 of the obtained IR spectrum with the calibration curve.
For 710T and CEANB, tablets were prepared in the same manner, IR spectra were measured, and the amount of hydroxyl groups on the surface of the fine particles was specified.

(III) Preparation of Organosiloxane Resin Paint [Reference Example 29]
To 133 parts by mass of an aqueous dispersion type colloidal silica dispersion (cataloid SN-30 manufactured by Catalyst Chemical Industry Co., Ltd., solid content concentration 30% by mass), 1.3 parts by mass of 1M hydrochloric acid was added and stirred well. This dispersion was cooled to 10 ° C., and 216 parts by mass of methyltrimethoxysilane was added dropwise under cooling in an ice-water bath. After the addition of methyltrimethoxysilane, the mixture was stirred at 30 ° C. for 10 hours, and then 1.1 parts by mass of a choline methanol solution (containing 45% by mass of choline), 6.7 parts by mass of acetic acid, and 220 parts by mass of isopropyl alcohol as a diluting solvent. The parts were mixed, and 51 parts by mass of 710T (IPA dispersion type titanium oxide dispersion liquid manufactured by Teika Co., Ltd.) was further added to obtain an organosiloxane resin coating material (ii-1).

[Reference Examples 30 to 37]
Organosiloxane resin paints (ii-2) to (ii-9) were obtained in the same manner as in Reference Example 28 except that the blending amount of 710T was as shown in Table 1.

SN-30: Cataloid SN-30 manufactured by Catalytic Chemical Industry Co., Ltd.
MTMOS: Methyltrimethoxysilane 710T: IPA-dispersed titanium oxide dispersion manufactured by TAYCA Corporation CEANB: IPA-dispersed cerium oxide dispersion manufactured by CIK Nanotech Co., Ltd. (CEANB 15 wt% E55)
MT-01: Titanium oxide fine powder manufactured by TAYCA CORPORATION

(IV) Preparation of laminated body [Example 1]
Acrylic resin paint (i-1) obtained in Reference Example 10 on a 5 mm thick polycarbonate resin (“Panlite” (registered trademark) manufactured by Teijin Limited, hereinafter referred to as PC) sheet as a base material layer. Was coated on both sides by a dip coating method so that the film thickness after thermosetting was 8 μm, allowed to stand at 25 ° C. for 20 minutes, and then thermoset at 130 ° C. for 1 hour. Next, the organosiloxane resin coating material (ii-1) obtained in Reference Example 28 was applied onto the film surface of the sheet by a dip coating method so that the film thickness after thermosetting was 4 μm, and the temperature was 25 ° C. for 20 minutes. After standing, it was heat-cured at 125 ° C. for 1 hour to obtain a PC resin molded body (laminated body) HC-1. The composition of HC-1 and the evaluation results are shown in Table 4.

[Examples 2 to 21, Comparative Examples 1 to 12]
PC resin molded bodies (laminated bodies) HC-2 to HC-21 were obtained in the same manner as in Example 1 except that the acrylic resin paint and the organosiloxane resin paint were changed to those shown in Table 4. Table 4 shows the composition of the obtained PC resin laminate and the evaluation results.

D': Content of D component with respect to 100 parts by weight of A component and B component G': Content of G component with respect to 100 parts by weight of E component and F component

The laminate of the present invention has a good appearance, and is excellent in adhesive resistance and boiling water resistance. It also exhibits extremely good weather resistance and wear resistance. Therefore, taking advantage of these characteristics, for example, glass and body of vehicles, windowpanes of construction machinery, windows, sashes and walls of buildings, houses, greenhouses, garages, roofs of arcades, headlight lenses, for optics. It can be suitably used for lenses, mirrors, eyeglasses, goggles, sound insulation walls, signal light lenses, curved mirrors, bike windshields, nameplates, various other sheets, films and the like.

Claims (12)

A laminate having a base material layer, a cured layer (P layer) of an acrylic resin composition, and a cured layer (T layer) of an organosiloxane resin composition in this order.
The acrylic resin composition is
(A) The following formula

(X in the formula (A) is at least one selected from the group consisting of a hydrogen atom and a methyl group, and Y is an alkyl group having 1 to 4 carbon atoms, a cycloalkyl group having 5 to 12 carbon atoms and a carbon number of carbon atoms. It is at least one group selected from the group consisting of 2 to 5 hydroxyalkyl groups, and the ratio of hydrogen atoms in X is 30 mol% or less, and the ratio of cycloalkyl groups in Y is 1 to 40 mol. %, The proportion of alkyl groups having 1 to 4 carbon atoms is 1 to 98 mol%, and the proportion of hydroxyalkyl groups having 2 to 5 carbon atoms is 1 to 15 mol%.)
Acrylic copolymer (component A) containing at least 70 mol% of the repeating unit represented by,
(B) It has a converted isocyanate group ratio of 5.5 to 50% by weight, and is 0.8 to 1.5 equivalents with respect to 1 equivalent of the hydroxy groups in the acrylic copolymer represented by the above formula (A). Amount of blocked polyisocyanate compound (B component),
(C) 0.001 to 0.4 parts by weight of the curing catalyst (C component) with respect to 100 parts by weight of the A component and B component in total, and (D) 100 parts by weight of the A component and B component in total. Contains 0.1 to 10 parts by weight of an amino-based silane coupling agent (component D) with respect to the portion.
The organosiloxane resin composition is
(E) Colloidal silica (E component), (F) Hydrolyzed condensate of alkoxysilane represented by the following formula (F) (F component), and R ¹ _m R ² _n Si (OR ³ ) _{4-m- n} (F)
In formula (F), R ¹ and R ² are independently selected from the group consisting of an alkyl group having 1 to 4 carbon atoms, a vinyl group, a methacryloxy group, an amino group, a glycidoxy group and a 3,4-epoxycyclohexyl group1. It is an alkyl group having 1 to 3 carbon atoms substituted with the above groups, R ³ is an alkyl group having 1 to 4 carbon atoms, and m and n are independently integers of 0, 1 and 2, respectively. And m + n is an integer of 0, 1, or 2.)
(G) Contains a metal oxide (G component),
The content of the E component is 10 to 60% by weight, the content of the F component is 40 to 90% by weight in terms of R ¹ _m R ² _n SiO _{(4-mn) / 2} , and the E A laminate in which the G component is 8 to 60% by weight with respect to 100 parts by weight of the total of the component and the F component. The laminate according to claim 1, wherein the triazine-based ultraviolet absorber residue in Y in the above formula (A) is contained in a proportion of 15 mol% or less. Regarding the acrylic resin composition, the following formula (H) of 1 to 40 parts by weight with respect to a total of 100 parts by weight of the A component and the B component.

(In the formula, R ⁴ is an alkyl group having 1 to 18 carbon atoms, a substituent represented by —CH ₂ CH (OH) CH _2OR ^{8 (where R 8 is} an alkyl group having 1 to 18 carbon atoms) or -CH (CH ₃ ) C (O) represents a substituent represented by O-R ⁹ (R ⁹ is an alkyl group having 1 to 18 carbon atoms), R ⁵ is a hydrogen atom and an alkyl group having 1 to 18 carbon atoms. Alternatively, it represents an alkoxy group having 1 to 18 carbon atoms, and R ⁶ and R ⁷ independently represent a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, an alkoxy group having 1 to 18 carbon atoms, or an alkoxy group having 1 to 18 carbon atoms. Represents a phenyl group which may be substituted with an alkyl group or a halogen atom, where V represents a hydrogen atom, an OH group or an alkyl group having 1 to 12 carbon atoms).
The triazine-based ultraviolet absorber (H component) represented by the above formula (A) is contained, and the total content of the triazine-based ultraviolet absorber residue in the formula (A) and the H component is 1 to 40 parts by weight. Item 2. The laminated body according to Item 1 or 2. The laminate according to any one of claims 1 to 3, wherein the content of the D component is 1.0 to 5.0 parts by weight with respect to 100 parts by weight of the total of the A component and the B component. .. The claim 1 to any one of claims 1 to 4, wherein the C component is at least one compound selected from the group consisting of an organic tin compound, an organic titanium compound, an organic zirconium compound, a tertiary amine compound and a quaternary ammonium salt compound. The laminate described. The laminate according to any one of claims 1 to 5, wherein the content of the G component is 10 to 45 parts by weight with respect to 100 parts by weight of the total of the E component and the F component. Claimed that the ratio of the content of the D component to the total 100 parts by weight of the A component and the B component and the content of the G component to the total 100 parts by weight of the E component and the F component is 15 to 200. Item 2. The laminate according to any one of Items 1 to 6. The laminate according to any one of claims 1 to 7, wherein the G component is at least one metal oxide selected from the group consisting of titanium oxide, zinc oxide, cerium oxide, tin oxide and tungsten oxide. Claimed that, when the cumulative 50% particle size and the cumulative 90% particle size in the laser diffraction particle distribution measurement of the G component are D50 and D90, respectively, D90 is 100 nm or less and D90 / D50 is 20 or less. The laminate according to any one of 1 to 8. The laminate according to claim 8 or 9, wherein the amount of hydroxyl groups on the surface of the metal oxide (G component) is 3.5 to 5 / nm ² as measured by an infrared absorption method. The laminate according to any one of claims 1 to 10, wherein the base material layer is made of a thermoplastic resin. A window glass formed from the laminate according to any one of claims 1 to 11.