JP2000108259A - Ultraviolet ray absorbing resin material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To improve the long period weatherability, the hardness of a surface, resistance to contamination and contamination removing property of a resin material by a method wherein a protecting layer, containing organic polymer composite inorganic micro-grain and a monomer produced by polymerizing a specified ultraviolet ray absorbing monomer, is provided on a substrate. SOLUTION: A substrate protecting layer, provided on at least one side of the resin substrate, contains inorganic polymer composite inorganic micro- grains and a polymer produced by polymerizing a monomer constituent containing at least one kind of monomer, selected from ultraviolet ray absorbing monomers shown by formula I and formula II. In the formula I, R1 is a hydrogen atom or a 1-8C hydrocarbon group, R2 is a lower alkylene group, R3 is hydrogen atom or methyl group, X is a hydrogen atom, a halogen, a 1-8C hydrocarbon atom, a lower alkoxy group, cyano group or nitro group. In the formula II, R4 represents a low class alkylene group, and R5 represents hydrogen atom or methyl group.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an ultraviolet-absorbing resin plate having excellent low-stainability and excellent stain-removal properties and excellent weatherability.

[0002]

2. Description of the Related Art Polycarbonate and other resin plates have excellent transparency, impact resistance, heat resistance, flame retardancy, etc., and are widely used in road building materials and building materials, and their use is expected to expand in the future. Have been. However, their use is limited because they are inferior in various surface properties such as surface hardness, stain resistance, and stain removal properties as compared with metals, glass, and the like, and there is a strong demand for improvement in resin sheet surface properties. As a method for improving the surface characteristics, for example, Japanese Patent Application Laid-Open No. 7-178335 discloses a technique for improving surface hardness and strength by using composite inorganic fine particles having an organic polymer fixed on the surface of inorganic fine particles as a film-forming composition. Proposed. The publication also discloses an ultraviolet absorber as an additive used in the film-forming composition.

[0003] It is considered that if various inorganic fine particles are contained in the surface layer and at the same time, an ultraviolet absorber is added for improving the weather resistance, good surface properties and weather resistance can be obtained. However, if the composite inorganic fine particles and the ultraviolet absorber are contained in the surface layer, these additives may bleed out from the surface layer over a long period of use, which is not necessarily sufficient for a long period of use. there were.

[0004]

SUMMARY OF THE INVENTION The present invention has been made in view of the above problems, and has as its object to provide excellent long-term weather resistance and excellent surface properties such as surface hardness, stain resistance, and stain removability. To provide a resin material.

[0005]

According to a first aspect of the present invention, there is provided a resin material having a base material protective layer on at least one side surface of a resin base material, wherein the base material protective layer is formed of an organic polymer composite inorganic material. A monomer containing fine particles (hereinafter sometimes referred to as “composite inorganic fine particles”) and containing at least one selected from ultraviolet absorbing monomers represented by the following general formulas (1) and (2) There is provided an ultraviolet absorbing resin material characterized by containing a polymer obtained by polymerizing components.

[0006]

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(Wherein, R ¹ is a hydrogen atom or a group having 1 to 1 carbon atoms)
8 represents a hydrocarbon group, R ² represents a lower alkylene group, R ³ represents a hydrogen atom or a methyl group, X represents a hydrogen atom, a halogen, a hydrocarbon group having 1 to 8 carbon atoms, a lower alkoxy group, a cyano group, Represents a group or a nitro group. )

[0008]

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Wherein R ⁴ represents a lower alkylene group;
R ⁵ represents a hydrogen atom or a methyl group. )

In order to further improve the long-term weather resistance, the monomer component further contains at least one selected from ultraviolet stable monomers represented by the following general formulas (3) and (4). Is preferred.

[0011]

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(Wherein, R ⁶ represents a hydrogen atom or a cyano group, R ⁷ and R ⁸ each independently represent a hydrogen atom or a methyl group, R ⁹ represents a hydrogen atom or a hydrocarbon group, and Y represents Represents an oxygen atom or an imino group.)

[0013]

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(Wherein, R ⁶ represents a hydrogen atom or a cyano group, R ⁷ , R ⁸ , R ^{7 ′} and R ^{8 ′} each independently represent a hydrogen atom or a methyl group, and Y represents an oxygen atom or an imino group. Represents a group.)

According to a second aspect of the present invention, there is provided a resin material having a base material protective layer on at least one side surface of a resin base material, wherein the base material protective layer contains organic polymer composite inorganic fine particles, An ultraviolet absorbing resin material is provided, wherein the resin base contains an ultraviolet absorbing agent.

In any of the above inventions, it is preferable that a primer layer is formed between the resin substrate and the substrate protective layer.

[0017]

BEST MODE FOR CARRYING OUT THE INVENTION The present inventors have conducted intensive studies on resin materials having excellent long-term weather resistance and excellent surface properties such as surface hardness, stain resistance and stain removal properties. A structure in which a base material protective layer is formed on the base material, and by including specific composite inorganic fine particles and a specific ultraviolet absorbing polymer in the base material protective layer, it is possible to improve the surface characteristics and at the same time to have long-term weather resistance, surface The inventors have found that the hardness, stain resistance and stain removal properties can be drastically improved, and have reached the first invention of the present application. Hereinafter, the configuration of the first invention of the present application will be described in detail.

The resin substrate used in the present invention is not particularly limited as long as it is a resin, and may be a plate-like body or an elastic body. The transparency, shape, molding method, thickness and the like are not particularly limited. Examples of usable resins include polycarbonate resin, acrylic resin, polyethylene resin, polyester resin, polypropylene resin, and ABS.
Resins, polystyrene resins, vinyl chloride resins and the like can be mentioned.

In the present invention, the compound is represented by the general formula (1).
The ultraviolet absorbing monomer represented by the formula: ¹ Is a hydrogen atom or
A hydrocarbon group having 1 to 8 carbon atoms;^Two Is lower al
Composed of a kylene group;^Three Is a hydrogen atom or a methyl group
X is hydrogen, halogen, hydrocarbon having 1 to 8 carbon atoms
Group, a lower alkoxy group, a cyano group or a nitro group.
Benzotriazoles formed.

In the above formula, examples of the substituent represented by R ¹ include a hydrogen atom, a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group and a tertiary group.
t-butyl group, pentyl group, hexyl group, heptyl group,
A chain hydrocarbon group such as an octyl group; a cyclopropyl group,
A cyclopentyl group, a cyclohexyl group, a cycloheptyl group, an alicyclic hydrocarbon group such as cyclooctyl group; a phenyl group, a tolyl group, a xylyl group, a benzyl group, an aromatic hydrocarbon group such as a phenethyl group, Table by R ² The substituent is specifically an alkylene group having 1 to 6 carbon atoms, such as a linear alkylene group such as a methylene group, an ethylene group, a trimethylene group, and a tetramethylene group; a propylene group; and 2-methyltrimethylene. Group, a branched alkylene group such as a 2-methyltetramethylene group, and the substituent represented by X is hydrogen; a halogen such as fluorine, chlorine, iodine, iodine; a methyl group, an ethyl group, a propyl group; Chain hydrocarbon groups such as isopropyl group, butyl group, isobutyl group, tert-butyl group, pentyl group, hexyl group, heptyl group and octyl group Alicyclic hydrocarbon groups such as cyclopropyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group and cyclooctyl group: aromatic hydrocarbon groups such as phenyl group, tolyl group, xylyl group, benzyl group and phenethyl group; methoxy group Ethoxy, propoxy, butoxy, pentoxy, heptoxy and the like; lower alkoxy groups having 1 to 6 carbon atoms; cyano groups; nitro groups.

The UV-absorbing monomer represented by the general formula (1) includes, for example, 2- [2'-hydroxy-5 '
-(Methacryloyloxymethyl) phenyl] -2H-
Benzotriazole, 2- [2'-hydroxy-5'-
(Methacryloyloxyethyl) phenyl] -2H-benzotriazole, 2- [2'-hydroxy-5'-
(Methacryloyloxypropyl) phenyl] -2H-
Benzotriazole, 2- [2'-hydroxy-5'-
(Methacryloyloxyhexyl) phenyl] -2H-
Benzotriazole, 2- [2'-hydroxy-3'-
tert-butyl-5 ′-(methacryloyloxyethyl) phenyl] -2H-benzotriazole, 2-
[2′-hydroxy-5′-tert-butyl-3′-
(Methacryloyloxyethyl) phenyl] -2H-benzotriazole, 2- [2'-hydroxy-5'-
(Methacryloyloxyethyl) phenyl] -5-chloro-2H-benzotriazole, 2- [2′-hydroxy-5 ′-(methacryloyloxyethyl) phenyl]
-5-methoxy-2H-benzotriazole, 2-
[2'-Hydroxy-5 '-(methacryloyloxyethyl) phenyl] -5-cyano-2H-benzotriazole, 2- [2'-hydroxy-5'-(methacryloyloxyethyl) phenyl] -5-tert-butyl −
2H-benzotriazole, 2- [2'-hydroxy-
5 '-(methacryloyloxyethyl) phenyl] -5
-Nitro-2H-benzotriazole and the like, but are not particularly limited thereto. One kind of these ultraviolet absorbing monomers represented by the general formula (1) may be used alone, or two or more kinds thereof may be appropriately mixed and used.

Further, in the ultraviolet absorbing monomer represented by the general formula (2), a substituent represented by R ⁴ is a lower alkylene group, and a hydrogen atom represented by R ⁵ or Benzotriazoles composed of a methyl group.

In the above formula, the substituent represented by R ⁴ is specifically an alkylene group having 2 or 3 carbon atoms, such as an ethylene group, a trimethylene group and a propylene group.

Examples of the ultraviolet absorbing monomer represented by the general formula (2) include 2- [2'hydroxy-5 '
-(Β-methacryloyloxyethoxy) -3′-te
rt-butylphenyl] -4-tert-butyl-2H
-Benzotriazole, but is not particularly limited thereto. Only one kind of these ultraviolet absorbing monomers represented by the general formula (2) may be used, or two or more kinds may be appropriately mixed.

In order to further improve the weather resistance, the monomer component used in the present invention is at least one kind selected from the ultraviolet stable monomers represented by the general formulas (3) and (4). Preferably, it further contains.

The general formulas (3) and (4) used in the present invention
In the UV-stable monomer, where R⁶ Indicated by
The substituent comprises a hydrogen atom or a cyano group;⁷ , R
⁸ , R ^{7 '}, R^{8 '}Each independently represent water
R or R⁹ Replacement indicated by
The group consists of a hydrogen atom or a hydrocarbon group and is represented by Y
Piper whose substituent is an oxygen atom or an imino group
Gins.

Specific examples of the substituent represented by R ⁹ include a hydrogen atom and a hydrocarbon group having 1 to 18 carbon atoms, such as methyl, ethyl, propyl, isopropyl, butyl, and isobutyl. Groups, tert-butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, etc. Alicyclic hydrocarbon groups such as cyclopropyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group and cyclooctyl group; phenyl group, tolyl group, xylyl group,
Non-limiting examples include aromatic hydrocarbon groups such as a benzyl group and a phenethyl group.

The UV-stable monomer represented by the general formula (3) includes, for example, 4- (meth) acryloyloxy-2,2,6,6-tetramethylpiperidine,
(Meth) acryloylamino-2,2,6,6-tetramethylpiperidine, 4- (meth) acryloyloxy-
1,2,2,6,6-pentamethylpiperidine, 4-
(Meth) acryloylamino-1,2,2,6,6-pentamethylpiperidine, 4-cyano-4- (meth) acryloylamino-2,2,6,6-tetramethylpiperidine, 4-crotonoyloxy- 2,2,6,6-tetramethylpiperidine, 4-crotonoylamino-2,
2,6,6-tetramethylpiperidine and the like,
One of these may be used alone, or two or more thereof may be appropriately mixed and used. Of course, the UV stable monomer of the general formula (3) is not limited to these compounds.

The UV-stable monomer represented by the general formula (4) includes, for example, 1- (meth) acryloyl-4
-(Meth) acryloylamino-2,2,6,6-tetramethylpiperidine, 1- (meth) acryloyl-4-
Cyano-4- (meth) acryloylamino-2,2,2
6,6-tetramethylpiperidine, 1-crotonoyl-
Examples thereof include 4-crotoyloxy-2,2,6,6-tetramethylpiperidine, and these may be used alone or in a combination of two or more. The UV-stable monomer of the general formula (4) is not limited to these.

The amount of the UV-absorbing monomer represented by the general formulas (1) and (2) is not particularly limited, but is desirably 1 to 90% by weight based on the UV-absorbing polymer. . Describing a more preferable range, the lower limit is preferably 5 wt%, more preferably 10 wt%. On the other hand, the upper limit is preferably 70 wt%, more preferably 50 wt%. If the amount of the UV-absorbing monomer is less than 1 wt%, it is necessary to increase the thickness of the substrate protective layer in order to prevent the resin substrate from being deteriorated by ultraviolet rays, and to form a surface protective layer thereon. Occasionally, cracks are likely to occur, and cracks may occur even after prolonged use. On the other hand, if it is more than 90 wt%, the physical properties of the base material protective layer may be reduced.

The amount of the UV-stable monomer represented by the general formulas (3) and (4) is not particularly limited, but is 0.1 to 0.1 with respect to the UV-absorbing polymer. 15wt
% Is desired. Describing a more preferable range, the lower limit is preferably 0.5 wt%, more preferably 1 wt%. On the other hand, the upper limit is preferably 5 wt%, more preferably 3 wt%. If the total amount of the UV-stable monomer is less than 0.1 wt%, the deterioration of the base material protective layer may not be prevented, while if it is more than 15 wt%, the physical properties of the base material protective layer may be reduced. May be caused.

Other copolymerizable unsaturated monomers other than the above-mentioned monomers do not impair various physical properties required for a polymer containing an ultraviolet absorbing monomer as a part of a repeating unit. Any of them can be used, and from the viewpoint of weather resistance, use of an unsaturated monomer represented by the following general formula (5) is preferred.

[0033]

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(In the formula, R ¹⁰ represents a hydrogen atom or a methyl group, and Z represents a hydrocarbon group having 4 or more carbon atoms.)

In the above formula, the substituent represented by Z is an alicyclic hydrocarbon group having 4 or more carbon atoms such as a cyclohexyl group, a methylcyclohexyl group, a cyclododecyl group; a butyl group, an isobutyl group, a tert-butyl group; Linear or branched alkyl groups having 4 or more carbon atoms such as 2-ethylhexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, pentadecyl, octadecyl; bornyl, isobornyl, etc. A polycyclic hydrocarbon group having 4 or more carbon atoms, among which an alicyclic hydrocarbon group, a branched alkyl group, and a straight-chain alkyl group having 6 or more carbon atoms are preferable.

As the unsaturated monomer represented by the general formula (5), for example, cyclohexyl (meth) acrylate, methylcyclohexyl (meth) acrylate, cyclododecyl (meth) acrylate, tert-butylcyclohexyl (meth) acrylate, isobutyl (Meth) acrylate, tert-butyl (meth) acrylate, lauryl (meth) acrylate, isobornyl (meth) acrylate, stearyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, and the like, and one or more of these. Can be used.

The amount of the unsaturated monomer represented by the general formula (5) is not particularly limited, but is preferably in the range of 3 to 70% by weight, more preferably 5 to 70% by weight based on the ultraviolet absorbing polymer.
-50 wt%. If the used amount is less than 3 wt%, it may be difficult to obtain desired weather resistance, while if it exceeds 70 wt%, the interlayer adhesion to the resin substrate may be reduced.

Other unsaturated monomers which can be copolymerized include carboxyl group-containing unsaturated monomers such as (meth) acrylic acid, itaconic acid, maleic acid and maleic anhydride;
-Acid phosphate unsaturated monomers such as (meth) acryloyloxyethyl acid phosphate; hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, caprolactone-modified hydroxy (meth) acrylate (for example, Daicel Chemical Industries, Ltd.) Unsaturated monomer containing a group having an active hydrogen such as manufactured by Co., Ltd. (trade name "Placcel FM"); methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate (Meth) acrylic acid lower alkyl esters such as glycidyl (meth) acrylate; epoxy group-containing unsaturated monomers; (meth) acrylamide, N, N'-dimethylaminotyl (meth) acrylate, imide (meth) acrylate Nitrogen-containing unsaturated Unsaturated monomers having two polymerizable double bonds such as ethylene glycol di (meth) acrylate; halogen-containing unsaturated monomers such as vinyl chloride and vinylidene chloride; styrene, α-methylstyrene, Examples thereof include aromatic unsaturated monomers such as vinyl toluene; vinyl esters such as vinyl acetate; and vinyl ethers, but are not particularly limited thereto. As the other monomer, only one kind may be used as needed, or two or more kinds may be used.

It is particularly preferable to use imide (meth) acrylate from the viewpoint of adhesion to the primer layer or the resin substrate.

The method of mixing the above monomers is not particularly limited, and a conventionally known mixing method can be employed.

The polymerization method for copolymerizing the monomer composition is not particularly limited, and a conventionally known polymerization method can be employed. For example, polymerization methods such as solution polymerization, dispersion polymerization, suspension polymerization, and emulsion polymerization can be used. Solvents that can be used when polymerizing the monomer composition using the solution polymerization method include toluene, xylene, and other aromatic solvents; iso-propyl alcohol, n-butyl alcohol, propylene glycol methyl ether,
Alcohol solvents such as dipropylene glycol methyl ether; ester solvents such as butyl acetate, ethyl acetate and cellosolve acetate; ketone solvents such as acetone, methyl ethyl ketone and methyl isobutyl ketone; dimethylformamide. Of course, solvents that can be used are not limited to these solvents, but solvents that erode the resin substrate are not preferred. These solvents may be used alone or in combination of two or more. The amount of the solvent used may be appropriately determined in consideration of the concentration of the product and the like.

When copolymerizing the monomer composition, a polymerization initiator is used. As the polymerization initiator, for example, 2,
2'-azobis- (2-methylbutyronitrile), te
rt-butylperoxy-2-ethylhexanoate,
Examples include ordinary radical polymerization initiators such as 2,2'-azobisisobutyronitrile, benzoyl peroxide, and di-tert-butyl peroxide. The amount of the polymerization initiator to be used should be appropriately determined from the required characteristic values of the polymer and the like, and is not particularly limited, but is preferably in the range of 0.01 to 50 wt% based on the total amount of the monomer components. Preferably, it is in the range of 0.05 to 20 wt%.

The reaction temperature is not particularly limited, but is preferably in the range of room temperature to 200 ° C, and is preferably 40 to 140 ° C.
Is more preferred. The reaction time may be appropriately set according to the composition of the monomer composition to be used, the type of the polymerization initiator, and the like so that the polymerization reaction is completed.

The weight average molecular weight (M
w) is not particularly limited, but 2,000 to 500,0.
00, more preferably 4,000 to 300,
5,000, more preferably 5,000 to 200,
000. Note that the weight average molecular weight is a value measured by polystyrene standard GPC.

The organic polymer composite inorganic fine particles used in the present invention mean composite inorganic fine particles in which an organic polymer is fixed on the surface of the inorganic fine particles. The contamination removal property is improved. The integration of the inorganic fine particles and the organic polymer may be achieved by fixing the organic polymer to the inorganic fine particles, and the inorganic fine particles are hydrolyzed and condensed by a silicon-containing polymer having an organic portion and an inorganic portion as described later. At the same time as forming the fine particles, integration with the organic polymer may be achieved. Here, fixing does not mean temporary adhesion and adhesion, but means that the organic polymer is not detected in the cleaning liquid when the composite inorganic fine particles are washed with a solvent. This strongly suggests that a chemical bond is formed between the polymer and the inorganic fine particles.

The inorganic fine particles that can be used may be fine particles substantially composed of an inorganic substance, regardless of the type of the constituent elements, but inorganic oxides are preferably used. The shape of the inorganic fine particles may be any shape such as a sphere, a needle, a plate, a scale, and a crushed shape, and is not particularly limited.

The average particle diameter of the composite inorganic fine particles is 5 to 200.
nm is preferable, and more preferably 5 to 100 nm.
Range. When the average particle diameter of the composite inorganic fine particles is less than 5 nm, the surface energy of the composite inorganic fine particles increases, and aggregation of the composite inorganic fine particles easily occurs. On the other hand, when the average particle size of the composite inorganic fine particles exceeds 200 nm, the transparency of the surface protective layer decreases. The variation coefficient (particle size distribution) of the particle diameter of the composite inorganic fine particles is 50% or less, and is 30% or less.
The following is preferred. This is because if the particle size distribution of the composite inorganic fine particles is too wide, that is, if the variation coefficient of the particle size exceeds 50%, the surface of the surface protective layer becomes very uneven, and the smoothness of the surface protective layer is lost.

The inorganic oxide is defined as various oxygen-containing metal compounds in which a metal element mainly forms a three-dimensional network through a bond with an oxygen atom. As the metal element constituting the inorganic oxide, for example, an element selected from Groups II to VI of the Periodic Table of the Elements is preferable, and an element selected from Groups III to V of the Periodic Table of the Elements is more preferable. Among them, Si, Al,
Elements selected from Ti and Zr are preferred. The metal element is S
The silica fine particles i are the most preferable inorganic fine particles because they are easy to produce and easily available. The inorganic oxide may contain an organic group or a hydroxyl group during the production thereof. The organic group is, for example, at least one selected from the group consisting of an optionally substituted alkyl group having 20 or less carbon atoms, a cycloalkyl group, an aryl group, and an aralkyl group.
Is a seed. The inorganic oxide constituting the inorganic fine particles need not be only one kind, but may be two or more kinds.

The organic polymer contributes to the improvement of the dispersibility of the inorganic fine particles in the resin and the affinity with the organic medium, and the organic polymer itself sometimes contributes as a binder or a matrix. The structure of the organic polymer is arbitrary, such as a linear, branched, or crosslinked structure. Examples of the resin constituting the organic polymer include (meth) acrylic resin, polystyrene, polyvinyl acetate, polyolefin such as polyethylene and polypropylene, vinyl chloride, vinylidene chloride, polyester such as polyethylene terephthalate, and copolymers thereof. May be a resin partially modified with a functional group such as an amino group, an epoxy group, a hydroxyl group or a carboxyl group. Among these, an organic polymer containing an acrylic unit such as an acrylic resin, an acrylic-styrene resin, and an acrylic-polyester resin has a layer forming ability and is suitable for a layer forming composition. Examples of the acrylic unit include methyl acrylate units, ethyl acrylate units, methyl methacrylate units, acrylate units having a hydroxyl group such as a polyethylene glycol side chain, and highly polar side chains such as a methacrylate unit having a hydroxyl group such as a polyethylene glycol side chain. Units which have, which improve the soil resistance and the decontamination properties of the layer.

The organic polymer may have a functional group. It is preferable that the functional group be a perfluoroalkyl group and / or a silicone group because the stain resistance and self-cleaning property of the layer are improved. The bonding state between the main chain of the organic polymer and the perfluoroalkyl group and / or silicone group is not particularly limited. In addition to those in which these groups are directly bonded to the main chain of the organic polymer, an ester group (-CO
O-) or those bonded via an ether group (-O-) or the like may be used. The content of the perfluoroalkyl group and / or the silicone group in the organic polymer is not particularly limited, but is preferably 0.01 to 50% of the total weight. If the content is less than 0.01%, migration of the composite inorganic fine particles to the surface of the layer during the formation of the film is unlikely to occur. On the other hand, if the content exceeds 50%, the composite inorganic fine particles may fall off from the surface of the layer, and the stain resistance and stain removal properties of the layer may be reduced.

Although the average molecular weight of the organic polymer is not particularly limited, it is preferably 200,000 or less, more preferably 50,000 or less, in consideration of solubility in an organic solvent, ease of production of composite inorganic fine particles, and the like. Is more preferred.

The composite inorganic fine particles used in the present invention may be any
It can be manufactured by a method. The organic part mentioned above and inorganic
When using a siloxane compound having a crystalline moiety
In this case, the siloxane compound used
Consisting of siloxane groups, at least one per molecule
Polysiloxane groups are bonded and the polysiloxane
At least one Si-OR in a xanth group¹ Group (R¹ Is
Substitution selected from a hydrogen atom or an alkyl group or an acyl group
At least one group which may be ¹ Is 1
When more than one R is present in the molecule,¹ Are identical to each other
Or different. )
Silicon polymers are preferred. Such silicon containing
Polymer alone or with a hydrolyzable metal compound
And a production method of hydrolysis and condensation.

The details of the composite inorganic fine particles and the production method thereof are described in JP-A-7-178335 and JP-A-9-30.
No. 2257, and the composite inorganic fine particles used in the present invention include those obtained by introducing an ethylenically unsaturated group into composite inorganic fine particles as described in Japanese Patent Application No. 9-291390. .

Commercial products of the resin containing the composite inorganic fine particles include, for example, “U-double C-3300” and “U-double C-3600” (all manufactured by Nippon Shokubai Co., Ltd.).
And the like.

Next, the formation of the base material protective layer will be described.
The produced ultraviolet-absorbing polymer and the above-mentioned composite inorganic fine particles are mixed with another polymer, if necessary, to obtain a base material protective layer composition, which is applied onto a resin base material. At this time, the base material protective layer is
It may be formed directly on the resin base material, or if the solvent for forming the base material protective layer dissolves the resin base material, it is preferable to form a primer layer on the surface of the resin base material and form the primer layer thereon. Good. Even when the solvent for forming the base material protective layer does not dissolve the resin base material, the further effect of the present invention can be exhibited by forming the primer layer. The primer layer is, for example, a layer having an adhesion promoting action made of a material selected from a silane coupling agent, a thermoplastic resin, a curable resin, or the like, and a layer having an action of preventing plastic transfer of the resin substrate.

As specific examples of the resin primer,
Polyester, polyamide, polyesteramide, polyvinyl acetal, vinyl chloride, poly (meth) acrylate, polyimide, polyurethane, polycarbonate, polystyrene, polymethylpentene, polyolefin, halogenated polyolefin as thermoplastic resin,
Alkyd resins, polyamide imides, silicon resins, fluorine resins and the like, and copolymers and mixtures thereof can be used. In addition, as the curable resin that is cured by light, heat, oxygen, or the like, for example, a phenol resin, a melamine resin, an epoxy resin, a crosslinkable organosilicon resin, or the like can be used. As the resin primer, a thermosetting resin is preferably used in view of the water resistance, solvent resistance, abrasion resistance, mechanical strength, and the like of the layer, and more preferably a resin primer that can be crosslinked by using a known crosslinking agent in combination.

In the present invention, it is desirable to use an epoxy resin, a polyester resin, or an acrylic resin copolymer resin among the above primers. For example, when the resin substrate is a soft vinyl chloride resin, Polyment NK-380 (manufactured by Nippon Shokubai Co., Ltd.) is used alone or in combination with an epoxy curing agent as a plasticizer inhibitor. In addition, as a solvent for the primer, an aqueous solvent may be used, but a well-known alcohol solvent, a carboxylic acid ester solvent, a ketone solvent, an aliphatic hydrocarbon, an alicyclic or aromatic hydrocarbon solvent, and a mixture thereof may be used. it can. Of course, solvents that can be used are not limited to these solvents, but solvents that erode the resin substrate are not preferred.

The thickness of the primer layer is not particularly limited.
It is preferably in the range of 0.01 to 50 microns, and in particular, 0.1 to 50 microns.
Those having a size in the range of 5 to 15 microns are preferred in terms of uniformity of formation of the primer layer, adhesion and the like.

The above composition is applied to a resin substrate by dipping,
Spraying, brush coating, curtain flow coater, gravure coating, roll coating, spin coating, bar coating, electrostatic coating and the like can be used. Thereafter, the applied base material protective layer is heated or irradiated with ultraviolet rays or electron beams to be cured to obtain a final molded product.

Here, when the produced ultraviolet absorbing polymer is a polymer which cannot be cured alone, it is necessary to add a curing agent. Such a curing agent contains two functional groups capable of crosslinking and curing with a curable functional group present in the ultraviolet absorbing polymer, for example, a hydroxyl group, an amino group, a carboxyl group or an anhydride thereof, an epoxy group or an amide group. The compound or polymer contained above is selected and used depending on the type of the functional group present in the ultraviolet absorbing polymer. For example,
When the functional group present in the ultraviolet absorbing polymer is a carboxyl group or an anhydride thereof, a cross-linking curing agent such as a polyisocyanate compound or a modified product thereof, an aminoplast resin, an epoxy resin, and an oxazoline group-containing resin; When the group is an epoxy group, an amine, a carboxylic acid,
Crosslinking curing agent comprising a compound containing amide, N-methylol alkyl ether, etc., and when the functional group is a hydroxyl group or an amino group, a crosslinking curing agent such as a polyisocyanate compound or a modified product thereof, an epoxy resin, an aminoplast resin, etc. Can be mentioned. Among these curing agents, isocyanate compounds, epoxy resins and aminoplast resins are preferable in combination with a group having active hydrogen.

As the other polymer to be mixed with the ultraviolet absorbing polymer, a thermoplastic polymer or a thermosetting polymer which can be crosslinked and cured alone or with a crosslinking agent can be used. The type and amount of the polymer may be appropriately determined depending on the use and required characteristics of the resin material of the present invention. As the polymer, for example, vinyl chloride resin,
Thermoplastic polymers such as polyester resin, acrylic resin, and silicone resin; thermosetting polymers that cure independently such as urethane resin, aminoplast resin, silicone resin, and epoxy resin; curing agents such as polyester resin, acrylic resin, and epoxy resin And a thermosetting polymer which is cured by the heat treatment.

The crosslinking curing agents may be used alone or in combination of two or more. The amount of the cross-linking curing agent used is appropriately determined depending on the type of the cross-linking curing agent and the like. Generally, the curable functional group present in the base material protective layer and the cross-linking curing reaction contained in the cross-linking curing agent are used. It is preferable that the molar ratio with the functional group to be used is in the range of 0.8 to 1.2. Further, a crosslinking catalyst may be added to promote the crosslinking reaction. Examples of such a crosslinking catalyst include salts, inorganic substances, organic substances, acid substances, and alkaline substances.

When the substrate protective layer is cured by heating, the curing temperature varies depending on the type of the crosslinkable functional group and the type of the curing agent used, but it is preferable to cure at a temperature of room temperature to 250 ° C., for example.

In the case of curing by irradiation with ultraviolet rays, the curing method varies depending on conditions such as the photopolymerization initiator used, the type of light source for generating ultraviolet rays, and the distance between the light source and the coated surface. 1,000-8,000
A method of irradiating 0 angstrom ultraviolet rays for several seconds or at most tens of seconds at the most can be mentioned.

When cured by electron beam irradiation,
For example, usually 50 to 1000 kev, preferably 100
With an acceleration voltage of ~ 300 keV, the absorption line is 1 ~ 20Mra
A method of irradiating an electron beam so as to be about d can be given. The electron beam irradiation may be performed in the air, but is preferably performed in an inert gas such as nitrogen.

After the irradiation with ultraviolet rays or the irradiation with electron beams, heating may be performed, if necessary, to further advance the curing.

The thickness of the base material protective layer is Lambert-B
Since it depends on the amount of the ultraviolet absorber to be copolymerized according to the eer's law, there is no particular limitation as long as the weather resistance of the desired resin base material and the performance of the surface protective layer are satisfied.
~ 200 microns is preferred, more preferably 1-10
0 microns, more preferably 2-30 microns. If the thickness is greater than 200 microns, the coating speed will be slow and the inherent performance of the resin substrate may be reduced.
On the other hand, if the thickness is less than 0.5 μm, it becomes difficult to apply the resin uniformly on the resin substrate, and the ultraviolet absorbing ability may be insufficient.

Next, the second invention of the present application will be described. The major feature of the second invention of the present application is that the resin material has a two-layer structure in which a base material protective layer is formed on a resin base material, and the base material protective layer contains organic polymer composite inorganic fine particles, and the resin base material has an ultraviolet absorber. Is contained. That is, by including the composite inorganic fine particles in the base material protective layer, excellent stain resistance and stain removal properties were obtained, and by using an ultraviolet absorber, excellent weather resistance was obtained. In addition, since the resin material has a two-layer structure and the resin base material contains an ultraviolet absorber, compared to the conventional resin material in which a single-layer structure resin material contains an ultraviolet absorber, the ultraviolet absorber has Bleed-out was suppressed and further long-term weather resistance was realized.

The ultraviolet absorbent used in the present invention is not particularly limited, and examples thereof include benzotriazole-based, benzophenone-based, salicylic acid phenyl ester-based, and triazine-based ultraviolet absorbers. Benzotriazole-based ultraviolet absorbers include 2- (5-methyl-
2-hydroxyphenyl) benzotriazole, 2-
[2-hydroxy-3,5-bis (α, α-dimethylbenzyl) phenyl] -2H-benzotriazole, 2-
(2′-hydroxy-5′-t-octylphenyl) benzotriazole, 2- (2′-hydroxy-5′-methylphenyl) benzotriazole, 2- (2′-hydroxy-5′-t-butylphenyl) Benzotriazole, 2,2-methylenebis [4- (1,1,3,3-tetramethylenebutyl) -6- (2Hbenzotriazol-2-yl) phenol] and the like, and benzophenone-based ultraviolet absorption As the agent, 2-hydroxy-4-octoxybensophenone, 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxy-
4'-chlorobenzophenone, 2,2-dihydroxy-
4-methoxybenzophenone, 2,2-dihydroxy-
4,4'-dimethoxybenzophenone and the like can be exemplified.

Examples of the salicylic acid phenyl ester ultraviolet absorber include para-t-butylphenyl salicylate and para-octylphenyl salicylate. Examples of the triazine ultraviolet absorber include:
2,4-diphenyl-6- (2-hydroxy-4-methoxyphenyl) -1,3,5-triazine, 2,4-diphenyl-6- (2-hydroxy-4-ethoxyphenyl) -1,3,3 5-triazine, 2,4-diphenyl-
6- (2-hydroxy-4-propoxyphenyl)-
1,3,5-triazine, 2,4-diphenyl-6
(2-hydroxy-4-butoxyphenyl) -1,3,3
5-triazine, 2,4-diphenyl-6- (2-hydroxy-4-hexyloxyphenyl) -1,3,5-
Triazine, 2,4-diphenyl-6- (21-hydroxy-4-octyloxyphenyl) -1,3,5-triazine, 2,4-diphenyl-6- (2-hydroxy-
4-dodecyloxyphenyl) -1,3,5-triazine, 2,4-diphenyl-6- (2-hydroxy-4-
Benzyloxyphenyl) -1,3,5-triazine,
2,4-diphenyl-6- (2-hydroxy-4-butoxyethoxy) -1,3,5-triazine and the like can be exemplified.

The amount of the ultraviolet absorber used is 1 to 35% by weight, more preferably 5 to 25% by weight, based on the resin base material.
More preferably, it is in the range of 10 to 20% by weight. If the amount is less than 1% by weight, the resin substrate may be deteriorated by ultraviolet rays. On the other hand, when the used amount exceeds 35% by weight, the ultraviolet absorber tends to bleed out from the resin substrate, and the transparency of the resin substrate may be impaired.

The means for incorporating the ultraviolet absorber into the resin substrate is not particularly limited. For example, by adding and mixing the ultraviolet absorber into the composition of the resin substrate and molding the resin substrate, An ultraviolet absorber can be included.

As the resin used for the base material protective layer, a thermoplastic resin or a thermosetting resin which can be crosslinked and cured alone or with a crosslinking agent can be used. Examples of the resin include a thermoplastic polymer such as a vinyl chloride resin, a polyester resin, an acrylic resin, and a silicone resin; a thermosetting polymer that cures alone such as a urethane resin, an aminoplast resin, and a silicone resin; a polyester resin and an acrylic resin And the like, a thermosetting polymer which is cured by a curing agent such as

The resin substrate and the composite inorganic fine particles used are the same as those of the first invention of the present application, and the method for forming the substrate protective layer on the resin substrate is also common.

In the first invention and the second invention of the present application,
The resin base material and the base material protective layer may further contain various additives. As an additive, for example, a leveling agent generally used in a composition for forming a layer such as a paint; graphite, molybdate orange, navy blue, cadmium-based pigment, titanium white, composite oxide pigment, transparent iron oxide, carbon black ,
Cyclic high-grade pigments, soluble azo pigments, copper phthalocyanine pigments,
Pigments such as dyed pigments and pigment intermediates; pigment dispersants; antioxidants; viscosity modifiers; light stabilizers; metal deactivators; peroxide decomposers; fillers; Agent; anticorrosive;
Rust inhibitors; fluorescent brighteners; organic and inorganic flame retardants; anti-dripping agents; melt flow modifiers; antistatic agents; silane coupling agents.

[0076]

The present invention will be described in more detail with reference to the following Examples and Comparative Examples, but the present invention is not limited thereto. Unless otherwise specified, "parts" described in Examples and Comparative Examples are parts by weight and "%"
Represents "% by weight".

(Synthesis of Polymer) (Synthesis Example 1) 40 parts of cyclohexyl methacrylate, 30 parts of butyl acrylate, and n-type were placed in a 500 ml flask equipped with a stirrer, a dropping port, a thermometer, a cooling tube, and a nitrogen gas inlet. 15 parts of butyl methacrylate, 15 parts of imide acrylate ("Aronix TO-1429" manufactured by Toagosei Co., Ltd.) and 80 parts of dipropylene glycol methyl ether were charged, and nitrogen gas was introduced, and the mixture was heated to 110 ° C while stirring. As an initiator, a mixture of 1 part of t-butylperoxy-2-ethylhexanoate and 20 parts of dipropylene glycol methyl ether was added dropwise to the charge over 2 hours, and after the addition, the mixture was heated for another 2 hours to give 49 parts of acrylic resin. A 9.9% solution was obtained.

This ultraviolet absorbing polymer is referred to as polymer 1. Table 1 shows the types and amounts of the monomer compositions and the characteristic values of the obtained polymers.

(Synthesis Examples 2 to 7) Polymers were produced in the same manner as in Synthesis Example 1 using the monomer compositions and compounding amounts shown in Table 1. The produced polymers are referred to as polymers 2 to 7, respectively. In Synthesis Examples 4 and 7, an ultraviolet absorbing polymer was synthesized in the same manner as in Synthesis Example 1, and a mixed gas of nitrogen and oxygen was introduced. , Tetraphenylphosphonium bromide 0.2
And a mixture of 0.01 part of methoquinone were added dropwise over 30 minutes, and the mixture was further reacted for 4 hours to produce Polymer 4 and Polymer 7 having an acroyl group in the side chain of the polymer.

[0080]

[Table 1]

UVA1: 2- [2'-hydroxy-5 '
-(Methacryloyloxyethyl) phenyl] -2H-
Benzotriazole UVA2: 2- [2′-hydroxy-5 ′-(β-methacryloyloxyethoxy) -3′-tert-butylphenyl] -4-tert-butyl-2H-benzotriazole HALS1: 4-methacryloyloxy-2 , 2,6,
6-tetramethylpiperidine HALS2: 1-methacryloyl-4-methacryloylamino-2,2,6,6-tetramethylpiperidine CHMA: cyclohexyl methacrylate TBMA: t-butyl acrylate MMA: methyl methacrylate BA: butyl acrylate n-BMA: n -Butyl methacrylate IA: imido acrylate HEMA: 2-hydroxyethyl methacrylate MAA: methacrylic acid GMA: glycidyl methacrylate Initiator: tert-butyl peroxy-2-ethylhexanoate Reaction solvent 1: n-butyl acetate Reaction solvent 2: di Propylene glycol methyl ether

(Production of Organic Polymer Composite Inorganic Fine Particles) Synthesis of Polymerizable Polysiloxane (S-1) Tetramethoxysilane 144.5 was placed in a 300 ml four-necked flask equipped with a stirrer, a thermometer and a condenser.
Parts, γ-methacryloxypropyltrimethoxysilane 2
3.6 parts, 19 parts of water, 30.0 parts of methanol, and 5.0 parts of a cation exchange resin (“Amberlyst 15” manufactured by Rohm and Haas) were added, and the mixture was stirred and reacted at 65 ° C. for 2 hours. . After the reaction mixture was cooled to room temperature, a distillation column was provided in place of the cooling tube, a cooling tube connected to the distillation column and an outlet were provided, and the temperature was raised to 80 ° C. over 2 hours under normal pressure until methanol did not flow out. It was kept at the same temperature. Further, the temperature was maintained at a pressure of 200 mmHg and a temperature of 90 ° C. until methanol no longer flowed out, and the reaction was further advanced. After cooling to room temperature again, "Amberlyst 15" was separated by filtration to obtain a polymerizable polysiloxane (S-1) having a number average molecular weight of 1,800.

Synthesis of Silicon-Containing Polymer (P-1) A 1-liter flask equipped with a stirrer, a dropping port, a thermometer, a cooling tube and a nitrogen gas inlet was charged with 200 parts of n-butyl acetate as an organic solvent. Gas was introduced, and the flask was heated to 110 ° C. while stirring. Next, a solution obtained by mixing 20 parts of polymerizable polysiloxane (S-1), 80 parts of methyl methacrylate, 80 parts of ethyl acrylate, 20 parts of 2-hydroxyethyl methacrylate, and 6 parts of 2,2′-azobisisobutyronitrile is dropped. 2 from the mouth
It was dropped over time. After the addition, the mixture was stirred at the same temperature for 1 hour, and then added with 1,1′-bis (t-butylperoxy) -3,
0.4 parts of 3 ', 5-trimethylcyclohexane was added twice every 30 minutes, and further heated for 2 hours to carry out copolymerization, and the silicon-containing polymer having a number average molecular weight of 13,000 was dissolved in n-butyl acetate. A solution was obtained. The solid content of the obtained silicon-containing polymer was 49.0%.

Synthesis of Silicon-Containing Polymer (P-2) A 0.5-liter flask equipped with a stirrer, a dropping port, a thermometer, a cooling tube and a nitrogen gas inlet was charged with 168 parts of ethanol as an organic solvent. Gas was introduced, and the flask was heated to 78 ° C. while stirring. Then, 16 parts of the polymerizable polysiloxane (S-1), 56 parts of methyl methacrylate, 56 parts of butyl acrylate, 32 parts of hydroxyethyl methacrylate, 2,2′-azobis (2,
A solution obtained by mixing 3.2 parts of 4-dimethylvaleronitrile) was dropped into the charge from the downflow port over 2 hours. After the addition of the above solution, the reaction mixture was continuously stirred at the same temperature for 1 hour, and then 0.3 parts of 2,2′-azobis (2,4-dimethylvaleronitrile) was added to the reaction mixture twice every 30 minutes. And the reaction mixture was heated for an additional 2 hours to effect copolymerization,
A silicon-containing polymer having a number average molecular weight of 9,000 (P-
A solution of 2) dissolved in ethanol was obtained. The solid content of the silicon-containing polymer (P-2) contained in the obtained solution was 4%.
0.0%.

Preparation of precursor (SZA-1) of composite inorganic fine particles n-butyl acetate was placed in a 500 ml four-necked flask equipped with a stirrer, two dropping ports (dropping port A and dropping port B), and a thermometer. 200 parts and 50 parts of methanol were charged, and the internal temperature was adjusted to 20 ° C. Then, while stirring the inside of the flask, n-acetic acid of the silicon-containing polymer (P-1) prepared above was used.
A mixed solution (raw material liquid A) of 20 parts of a butyl solution, 30 parts of tetramethoxysilane, and 20 parts of n-butyl acetate (a raw material liquid A) was added through a dropping port A to a mixed liquid (raw material liquid B) of 20 parts of 25% aqueous ammonia and 20 parts of methanol. The solution was dropped over 1 hour from the dropper. After dropping, stirring was continued at the same temperature for 2 hours to obtain a composite inorganic fine particle dispersion (SZ-1).

The precursor (SZ-1) of the composite inorganic fine particles obtained above was placed in a 500-ml four-necked flask equipped with a stirrer, a thermometer, a cooling pipe, and a distillation column connected to an outlet.
, And the flask was heated to 100 ° C. under a pressure of 110 mmHg, and ammonia, methanol, acetic acid n
-Butyl was distilled off until the solid content concentration became 30%, and a dispersion of composite inorganic fine particles dispersed in n-butyl acetate (SZA
-1) was obtained.

Production of Composite Inorganic Fine Particles (SZB-1) Ethanol 627 was placed in a 1-liter four-necked flask equipped with a stirrer, two dropping ports (dropping ports A and B), and a thermometer.
The internal temperature was adjusted to 20 ° C. Then, an ethanol solution 3 of the silicon-containing polymer (P-2) was added to this charge.
A mixture of 2 parts and 70 parts of tetramethoxysilane (raw material liquid A) was stirred through a dropping port A, and a mixed liquid of 9% of 25% ammonia water, 36 parts of ethanol and 27 parts of water (raw material liquid B) was stirred through a dropping port. While dropping over 1 hour. After the dropwise addition, the reaction mixture was stirred at the same temperature for 30 minutes, and then 3-methacryloxypropyltrimethoxysilane was added to the reaction mixture.
A liquid mixture (raw material liquid C) of 10 parts of ethanol and 10 parts of ethanol was dropped from the dropping port a over 15 minutes. The reaction mixture was further stirred for 30 minutes to obtain a composite inorganic fine particle dispersion (SZ-1) in which the composite inorganic fine particles were dispersed.

Next, a device equipped with a stirrer, a dropping port and a thermometer was prepared.
400 parts of the composite inorganic fine particle dispersion (SZ-1) obtained above, 20 parts of "Nonipol 200" (manufactured by Sanyo Kasei Co., Ltd.) as a surfactant, and 100 parts of water were charged into a four-neck four-liter flask, The internal temperature was adjusted to 100 ° C., and ammonia, ethanol, and methanol were distilled off until the solid content concentration of the charge became 30% to obtain a composite inorganic fine particle dispersion (SZB-1) in which the composite inorganic fine particles were dispersed in water. Obtained.

The resulting dispersions (SZA-1, SZB-
Table 2 shows the concentration of the composite inorganic fine particles of 1), the content of the inorganic substance in the composite inorganic fine particles, the average particle diameter and the variation coefficient of the composite inorganic fine particles, the content of the alkoxy group in the composite inorganic fine particles, and the stability over time.
Shown in

The obtained composite inorganic fine particles (SZA-1, SZA-1
ZB-1) was centrifuged to obtain a supernatant,
Analysis by PC revealed no organic polymer.
Further, the composite inorganic fine particles, which are precipitates after the centrifugation, are
After washing with HF or water, the washing solution was analyzed by GPC, but no organic polymer was detected. The above results indicate that in the composite inorganic fine particles, the organic polymer is not simply attached to the inorganic fine particles but is firmly fixed.

[0091]

[Table 2]

Evaluation of Composite Inorganic Fine Particles The composite inorganic fine particle dispersion obtained above was evaluated for the composite inorganic fine particle concentration, the inorganic content in the composite fine particles, the average particle size and the variation coefficient of the composite inorganic fine particles, the alkoxy fine particles in the composite inorganic fine particles. The group content and the stability over time were analyzed and evaluated by the following methods.

Concentration of Composite Inorganic Fine Particles
It was dried at 0 ° C. for 24 hours and calculated from the following equation. Composite inorganic fine particle concentration (% by weight) = 100 × D / W (where D: weight of composite inorganic fine particles after drying (g),
W: Weight of the composite inorganic fine particle dispersion before drying (g)

Inorganic Content in Composite Inorganic Fine Particles The composite inorganic fine particle dispersion was treated under a pressure of 100 mmHg at 13
Elemental analysis was performed on the product dried at 0 ° C for 24 hours.
The ash content was defined as the inorganic content in the composite inorganic fine particles.

Average Particle Size and Coefficient of Variation Measured at 23 ° C. by dynamic light scattering measurement using the following apparatus. The measured average particle diameter is a volume average particle diameter.

Apparatus: Submicron particle size analyzer (“NICOMP MODEL 370” manufactured by Nozaki Sangyo Co., Ltd.) Measurement sample: Composite inorganic fine particle concentration of 0.1 to 2.0% by weight
(In the case where the organic polymer in the composite inorganic fine particles is not dissolved in tetrahydrofuran, the composite inorganic fine particle dispersion is dispersed in a solvent in which the organic polymer is dissolved). Coefficient of variation: The coefficient of variation is calculated from the following equation. Coefficient of variation (%) = (standard deviation of particle diameter of composite inorganic fine particles)
/ (Average particle diameter of composite inorganic fine particles)

Alkoxy Group Content in Composite Inorganic Fine Particles
5 parts dried at 0 ° C. for 24 hours are mixed with 50 parts of acetone and 2N
Dispersed in a mixture of 50 parts of an aqueous NaOH solution,
Stir for 4 hours. Thereafter, the alcohol in the liquid was quantified using a gas chromatograph, and the alkoxy group content of the composite inorganic fine particles was calculated.

Stability over time The obtained dispersion was sealed in a Gardner viscosity tube,
Stored at 50 ° C. One month later, those in which no aggregation, sedimentation or increase in viscosity of the particles were observed were evaluated as “○”.

Example 1 To 100 parts of the polymer 1 obtained in Synthesis Example 1, 0.01 part of a leveling agent (“BYK300” manufactured by Big Chemie Co.) was added, and the mixture was thoroughly stirred. The solution was prepared. Next, the surface of the polycarbonate resin plate was washed with ethyl alcohol, the acrylic resin solution was applied to the surface of the polycarbonate resin plate so that the coating film thickness became 5 μm, air-dried, and then heat-cured at 80 ° C. for 30 minutes. . Next, the composite inorganic fine particles (S) prepared as described above were adjusted so that the inorganic oxide content was 10% in 100 parts of the resin of the polymer 5.
The curing agent B is blended with the mixed solution obtained by mixing ZA-1) such that the molar ratio of the hydroxyl group contained in the mixed solution to the isocyanate group contained in the curing agent B is 1: 1 and the leveling agent ( "BYK300" manufactured by Big Chemie) 0.0
One part was added and stirred well, and an acrylic resin solution was adjusted to a predetermined viscosity. The solution is applied to the surface of the polycarbonate resin plate on which the primer layer has been applied so that the thickness of the coating film becomes 5 μm, and thermally cured at 100 ° C. for 30 minutes.
Test plates were made. The obtained test plate was evaluated for evaluation items described later.

Example 2 The composite inorganic fine particles (SZA-1) produced as described above such that the content of the inorganic oxide in the resin of the polymer 6 was 10%.
And a leveling agent ("BYK300" Big Chemie) in which a hydroxyl group contained in the mixture and an isocyanate group contained in the curing agent A are mixed at a molar ratio of 1: 1. (Manufactured by K.K.) and stirred well to prepare an acrylic resin solution so as to have a predetermined viscosity. The solution was applied to the surface of the vinyl chloride resin plate on which the primer layer was not formed so that the thickness of the coating film became 5 μm, and was thermally cured at 80 ° C. for 30 minutes to prepare a test plate. The obtained test plate was evaluated for evaluation items described later.

Example 3 In the same manner as in Example 1, a plasticizer transfer inhibitor "NK-380" (manufactured by Nippon Shokubai Co., Ltd.) and a curing agent C were combined on a resin substrate shown in Table 3. Then, a base layer was formed and a test plate was prepared and evaluated in the same manner as in Example 2. Table 3 shows the evaluation results.

Example 4 A primer layer was formed on the surface of a resin substrate in the same manner as in Example 1 except that 100 parts of the polymer 2 obtained in Synthesis Example 2 was used and 7 parts of the curing agent A was used. Next, 100 of polymer 7
The composite inorganic fine particle dispersion (SZA-1) produced above was added so that the content of the inorganic oxide became 10% in the part, and a leveling agent ("BYK300" manufactured by Big Chemie) was further added.
0.01 part was added and the mixture was stirred well, and the acrylic resin solution was adjusted to a predetermined viscosity. The solution is coated on the primer layer so that the coating thickness becomes 20 microns,
For 10 minutes. Thereafter, irradiation was performed using an area beam type electron beam irradiation apparatus (manufactured by Nissin High Voltage) under a nitrogen atmosphere under the conditions of an acceleration voltage of 200 kV and a dose of 10 Mrad. Was. Table 3 shows the evaluation results.

Example 5 A primer layer was formed on the surface of a resin substrate in the same manner as in Example 4 except that 100 parts of the polymer 3 obtained in Synthesis Example 3 was used. Next, the above-prepared composite inorganic fine particle dispersion (SZB-1) was added to 100 parts of the polymer 4 so that the inorganic oxide content became 10%, and a leveling agent (“BY
K300 (manufactured by Big Chemie Co., Ltd.) (0.01 part) was added and stirred well to prepare an acrylic resin solution to a predetermined viscosity. The solution was applied on the primer layer so that the coating thickness became 10 μm, and dried at 80 ° C. for 10 minutes.
Then, using an area beam type electron beam irradiator (manufactured by Nissin High Voltage) under an atmosphere of nitrogen and an acceleration voltage of 200 k
Irradiation was performed under the conditions of V and a dose of 10 Mrad, electron beam curing was performed, and a test plate was prepared and evaluated. Table 3 shows the evaluation results.

Comparative Example 1 A test plate was prepared and evaluated in the same manner as in Example 1 except that the composite inorganic fine particles were not added. Table 3 shows the evaluation results.

Comparative Example 2 Additive type UV absorber ("MARK LA31" Adeka
Argus Chemical Co., Ltd.) to polymer 4 (solid content)
A test plate was prepared and evaluated in the same manner as in Example 4 except that wt% was added, the coating film thickness was set to 20 μm, and electron beam curing was performed. Table 3 shows the evaluation results.

Comparative Example 3 A test plate was prepared and evaluated in the same manner as in Example 5, except that the additive type ultraviolet absorber was not added to the resin base material layer and the coating thickness of the base material protective layer was changed to 5 μm. Was done. Table 3 shows the evaluation results.

(Stain resistance) A 0.05% aqueous solution of carbon was applied to the film 30 times with a brush, and the solution was forcibly dried at 80 ° C. for 1 hour, and then washed 30 times with a brush while washing with water. The degree was visually evaluated according to the following criteria. ：: No adhesion ○: Almost no adhesion △: Some adhesion x: Adhesion

(Contamination Removal Property) A test plate was exposed to south (30 °) in Suita-shi, Osaka, and the coating film was formed using an integrated spectral colorimeter (manufactured by JEOL Ltd.) in accordance with JISZ8730. The initial lightness and the lightness of the film after 3 months and 6 months were measured, and the difference (ΔL) was evaluated as an index of the decontamination property. The closer the ΔL value is to zero, the less the stain is.

(Gloss retention property) Using a sunshine weather meter (manufactured by Suga Test Instruments Co., Ltd.), the test plate was subjected to a cycle of 2 hours without rainfall and 18 minutes of rainfall at a constant temperature of 63 ° C. for 3,000 hours. After the exposure, the gloss (angle 60 °) of the test plate before and after the exposure was measured, and the gloss retention was evaluated.

(Yellowness) Based on JISK-7103,
The yellowness indicating the coloring (particularly yellowishness) of the test plate at an ambient temperature of 23 ° C. before and after the weather resistance test was measured, and the difference was evaluated as the yellowing degree. When the yellowing degree exceeds 4, it can be visually recognized that coloring has occurred.

(Surface Hardness) A pencil scratch test (pencil hardness test) in accordance with JIS K5400 6.14 was performed, and evaluation was carried out for scratches.

[0112]

[Table 3]

NK-380: plasticizer migration inhibitor (“Polyment NK-380” manufactured by Nippon Shokubai Co., Ltd.) Curing agent A: polyfunctional isocyanate (“Sumidur N-
3200 "manufactured by Sumitomo Bayer Urethane Co., Ltd. Curing agent B: blocked isocyanate (" Duranate M
F-K60X, manufactured by Asahi Kasei Kogyo Co., Ltd.) Curing agent C: bisphenol A type epoxy (“Epicoat 828” manufactured by Yuka Shell) Leveling agent: “BYK300” manufactured by Big Chemie Polycarbonate (UVA): polycarbonate resin (“Teflon IV 2500” Idemitsu) Petrochemical 90w
A polycarbonate resin plate obtained by mixing t% and 15 wt% of an additive type ultraviolet absorber (“MARK LA31” manufactured by Adeka Argus Chemical Co., Ltd.) and extruding the mixture.

The resin materials of Examples 1 to 4 containing the composite inorganic fine particles and the ultraviolet absorbing polymer in the base material protective layer are excellent in the balance between surface hardness, stain resistance and stain removal properties, and even after the weather resistance test. The gloss was maintained and the yellowing degree was also a small value. In particular, in Examples 1, 3, and 4 in which the primer layer was formed between the resin substrate and the substrate protective layer, excellent results were obtained. The resin material of Example 5 in which the resin base material contains an ultraviolet absorber and the base material protective layer contains composite inorganic fine particles,
The yellowing degree was higher than that of the other examples using the UV absorbing polymer, but at a practical level, and the surface hardness, stain resistance and stain removal properties, and gloss retention were excellent. The value was shown. On the other hand, in the resin material of Comparative Example 1 in which the composite inorganic fine particles are not contained in the base material protective layer, although the yellowing degree shows a small value, the surface hardness, the stain resistance and the stain removal property are poor, and the base material protective layer In addition, the resin material of Comparative Example 2 containing an additive type ultraviolet absorber had poor stain resistance and stain-removability after 6 months, and was also inferior in surface hardness, gloss retention and yellowing degree. In the resin material of Comparative Example 3 which contains the composite inorganic fine particles in the base material protective layer but does not contain the ultraviolet absorbing polymer or the ultraviolet absorbing agent, excellent effects are observed in the surface hardness, stain resistance and stain removal property. However, the yellowing degree is 15
And yellowish color developed so as to be clearly recognized by visual observation.

[0115]

The ultraviolet-absorbing resin material of the present invention has excellent long-term weather resistance and various surface characteristics such as surface hardness, stain resistance, and stain removal properties. It can be widely used in places where metal, glass and the like are conventionally used, such as building materials such as wall plates in tunnels and signs, and road building materials.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C09D 5/32 C09D 5/32 7/12 7/12 Z 139/04 139/04 (72) Inventor Aoyama Takahiro 5-8 Nishiomibashi-cho, Suita-shi, Osaka F-term (reference) in Nippon Shokubai Co., Ltd. 4D075 CA32 CA34 CB07 DA04 DA06 DB31 DC01 DC05 DC13 EB11 4F100 AA20 AH03 AK45 AK52 BA02 BA03 BA05 BA06 BA13 CA02 CA18 EH46 GB07 GB90 JK14 JL06 JL09

Claims (4)

[Claims] 1. A resin material having a substrate protective layer on at least one side surface of a resin substrate, wherein the substrate protective layer contains organic polymer composite inorganic fine particles, and has the following general formula (1): An ultraviolet-absorbing resin material comprising a polymer obtained by polymerizing a monomer component containing at least one selected from ultraviolet-absorbing monomers represented by (2). Embedded image (Wherein, R ¹ represents a hydrogen atom or a hydrocarbon group having 1 to 8 carbon atoms, R ² represents a lower alkylene group, R ³ represents a hydrogen atom or a methyl group, X represents a hydrogen atom, a halogen,
Represents a hydrocarbon group having 1 to 8 carbon atoms, a lower alkoxy group, a cyano group or a nitro group. ) (In the formula, R ⁴ represents a lower alkylene group, and R ⁵ represents a hydrogen atom or a methyl group.) 2. The ultraviolet absorbing resin material according to claim 1, wherein said monomer component further contains at least one selected from ultraviolet stable monomers represented by the following general formulas (3) and (4). . Embedded image (Wherein, R ⁶ represents a hydrogen atom or a cyano group, R ^7,
R ⁸ each independently represents a hydrogen atom or a methyl group; R ⁹ represents a hydrogen atom or a hydrocarbon group; and Y represents an oxygen atom or an imino group. ) (Wherein, R ⁶ represents a hydrogen atom or a cyano group, R ^7,
R ⁸ , R ^{7 ′} and R ^{8 ′} each independently represent a hydrogen atom or a methyl group, and Y represents an oxygen atom or an imino group. ) 3. A resin material having a base material protective layer on at least one side surface of a resin base material, wherein the base material protective layer contains organic polymer composite inorganic fine particles, and the resin base material is an ultraviolet absorbent. An ultraviolet-absorbing resin material comprising: 4. The ultraviolet absorbing resin material according to claim 1, wherein a primer layer is formed between said resin substrate and said substrate protective layer.