JP2002254544A - Thermoplastic resin laminate - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a thermoplastic resin laminate excellent not only in surface gloss, scratch resistance, weatherability and resistance against hot water or a solvent but also in mechanical strength or impact resistance. SOLUTION: The thermoplastic resin laminate has a layer based on a thermoplastic resin (A) with a pencil scratch test value of H or more, which has a lactone ring structure formed by the cyclization condesnation reaction of a polymer having a hydroxyl group and an ester group in its molecular chain, and a layer based on a thermoplastic resin (B) with a pencil scratch test value of <H and an Izod impact strength of 10 kJ/m<2> or more. The thickness of the layer based on the thermoplastic resin (A) is 10-5,000 μm. Concretely, the layer based on the thermoplastic resin (B) contains at least one kind of the thermoplastic resin (B) selected from a polycarbonate resin, a rubber reinforced styrene resin and a vinyl chloride resin as a main component.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a thermoplastic resin laminate having excellent surface gloss, scratch resistance, weather resistance, resistance to hot water and solvents, and excellent mechanical strength and impact resistance. is there.

[0002]

2. Description of the Related Art Since (meth) acrylic resins have excellent transparency, surface gloss and weather resistance and have relatively high surface hardness, they have been used as surface layers of various resins by making use of their characteristics. In particular, laminates in combination with rubber-reinforced styrene resins such as polycarbonate resins and ABS resins having excellent impact resistance have been widely used.

[0003] Polycarbonate resins are excellent in impact resistance, transparency and heat resistance and are used for various purposes. For example, extruded sheets are carports,
It is widely used in industrial fields such as signboards, architectural glazing materials, glazing materials for various vehicles, and soundproof walls. However, the polycarbonate resin alone is inferior in surface properties such as weather resistance, abrasion resistance, and solvent resistance, and various methods have been proposed as a method for improving the same.

As a means for improving the weather resistance of polycarbonate, a method of coating the surface of the polycarbonate with an acrylic resin containing an ultraviolet absorber (Japanese Patent Publication No. 47-19 / 1976)
119, JP-A-55-59929, JP-A-2-175
No. 245, JP-A-4-270652) has been proposed, but this method improves the weather resistance but does not improve the solvent resistance or the scratch resistance.

On the other hand, as a method for improving the scratch resistance and solvent resistance of polycarbonate, a method of coating a thermosetting resin such as an organosiloxane type or a melamine type or a polyfunctional acrylic type photocurable resin is adopted. However, with this method, it is difficult to reduce costs and improve productivity.

As with polycarbonate, ABS resin, AE
Rubber-reinforced styrene resins such as S resin, ACS resin and AAS resin are also excellent in impact resistance and excellent in balance between mechanical properties such as mechanical strength and workability, so they are used in vehicles, household goods, and miscellaneous goods. Are used in a wide range of fields such as general equipment. However, these rubber-reinforced styrenic resins have the disadvantages that they contain a rubbery polymer, have a low surface hardness, are easily damaged, and have a slight effect on the quality of the surface. As a means for improving these surface characteristics, for example, a method of coating an ABS resin surface with an acrylic resin has been proposed.

Japanese Patent Application Laid-Open No. 10-50258 discloses that when a laminate of an ABS resin and an acrylic resin is used for a sheet for sanitary articles such as a bathtub or a wash basin, the resistance to hot and cold water and the resistance to stress cracking to alcohol are improved. However, even this method has not been satisfactory with respect to the solvent resistance.

As a means for improving the surface characteristics of the ABS, there are methods of painting the surface or coating the surface, but there are many problems in terms of cost and productivity.

[0009]

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to improve the above-mentioned conventional problems, to provide excellent surface gloss, abrasion resistance, weather resistance, resistance to hot water and solvents, mechanical strength and the like. An object of the present invention is to provide a thermoplastic resin laminate excellent in impact resistance at high productivity and at low cost.

[0010]

Means for Solving the Problems The present inventors have conducted intensive studies to solve these problems, and as a result, they have obtained a polymer having a hydroxyl group and an ester group in a molecular chain by a cyclocondensation reaction. It has a lactone ring structure formed and has a pencil scratch test value (measured according to JIS-K 5400) of H
The above-mentioned layer mainly composed of the thermoplastic resin (A), the pencil scratch test value is less than H, and the Izod impact strength (measurement according to ASTM-D-256, notched, thickness 3. 2 mm) is 10 kJ / m ² or more and has a layer mainly composed of the thermoplastic resin (B), and the layer mainly composed of the thermoplastic resin (A) has a thickness of 10 μm to 50 μm.
A configuration of a thermoplastic resin laminate characterized by being in the range of 00 μm is proposed. More specifically, the thermoplastic resin (B) is preferably at least one thermoplastic resin selected from a polycarbonate resin, a rubber-reinforced styrene resin, and a vinyl chloride resin.

Similarly, a (meth) acrylic thermoplastic resin (A) having a lactone ring structure formed by a cyclocondensation reaction of a polymer having a hydroxyl group and an ester group in the molecular chain. And a layer mainly composed of at least one thermoplastic resin (B) selected from a polycarbonate resin, a rubber-reinforced styrene resin and a vinyl chloride resin, wherein the thermoplastic resin ( The thickness of the layer mainly composed of A) is from 10 μm to 5000
A structure of a thermoplastic resin laminate characterized by being in the range of μm is proposed.

More preferably, the lactone ring structure of the thermoplastic resin (A) is a structure represented by the following general formula (1).

[0013]

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(In the above formula (1), R ¹ , R ² and R ³
Each independently represents a hydrogen atom or an organic residue having 1 to 20 carbon atoms. The organic residue may contain an oxygen atom. More preferably, the thermoplastic resin (A) is a thermoplastic resin laminate containing a methyl methacrylate monomer unit. More specifically, a sheet in which the ratio of the thickness of the layer mainly containing the thermoplastic resin (A) to the thickness of the layer mainly containing the thermoplastic resin (B) is 1/99 to 50/50. By adopting the above configuration which is a thermoplastic resin laminate in a shape of a surface, surface gloss, scratch resistance, weather resistance, excellent resistance to hot water and solvents, and excellent mechanical strength and impact resistance The present inventors have found that a thermoplastic resin laminate can be obtained, and that the thermoplastic resin laminate can be obtained at high productivity and at low cost by coextrusion molding, thereby completing the present invention.

[0015]

BEST MODE FOR CARRYING OUT THE INVENTION The thermoplastic resin laminate of the present invention
It has a lactone ring structure formed by a cyclocondensation reaction of a polymer having a hydroxyl group and an ester group in its molecular chain, and has a pencil scratch test value (measured according to JIS-K 5400) of H or more. A layer containing a thermoplastic resin (A) as a main component and a pencil scratch test value (JIS-K5
A thermoplastic resin (B) having an Izod impact strength (measured according to ASTM-D-256, notched, 3.2 mm in thickness) of 10 kJ / m ² or more; Are laminated. More specifically, it is a thermoplastic resin laminate in which the thickness of the layer mainly containing the thermoplastic resin (A) is in the range of 10 μm to 5000 μm. Hereinafter, each layer will be described.

<Layer Containing Thermoplastic Resin (A) as Main Component> The thermoplastic resin (A) is obtained by subjecting a polymer (a) having a hydroxyl group and an ester group in a molecular chain to a cyclocondensation reaction. It is a thermoplastic resin having a lactone ring structure formed. Specifically, the lactone ring structure is preferably a structure represented by the following general formula (1).

[0017]

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(In the formula (1), R ¹ , R ² and R ³ are
Each independently represents a hydrogen atom or an organic residue having 1 to 20 carbon atoms. The organic residue may contain an oxygen atom. In order to form the lactone ring structure represented by the general formula (1), the polymer (a) having a hydroxyl group and an ester group in the molecular chain includes, for example, a (meth) acrylate monomer Preferable examples include a polymer obtained by polymerizing a monomer component containing (a1) and a vinyl monomer (a2) having a structural unit represented by the following general formula (2).

[0019]

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(In the formula (2), R ⁴ and R ⁵ each independently represent a hydrogen atom or an organic residue having 1 to 20 carbon atoms.) The (meth) acrylate monomer (a1) is There is no particular limitation as long as it is a so-called (meth) acrylic acid alkyl ester monomer other than the vinyl monomer having a 2- (hydroxymethyl) acrylic acid ester structural unit represented by the general formula (2). . For example, an aliphatic (meth) acrylate having an alkyl group or the like, an alicyclic (meth) acrylate having a cyclohexyl group or the like, or an aromatic (meth) acrylate having a benzyl group or the like may be used. Also, a desired substituent or functional group may be introduced into these groups.

The (meth) acrylate monomer (a)
Specific examples of 1) include, for example, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, (meth)
(Meth) such as n-butyl acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, and benzyl (meth) acrylate Acrylic esters and the like can be mentioned. These may be used alone or in combination of two or more. Among these, methyl methacrylate and methyl acrylate are preferable in terms of weather resistance, surface gloss, and transparency of the obtained thermoplastic resin (A), and more preferable in terms of surface hardness of the obtained thermoplastic resin (A). Preferably, methyl methacrylate is good. The (meth) acrylate having a cyclohexyl group imparts hydrophobicity to the thermoplastic resin (A), and as a result, the water absorption of the thermoplastic resin (A) can be reduced. Is preferred in that it can provide Further, a (meth) acrylate having an aromatic group is preferable because the aromatic ring can further improve the heat resistance of the thermoplastic resin (A) obtained.

The proportion of the (meth) acrylate monomer (a1) in the monomer component is not particularly limited, but is preferably from 95 to 10% by weight, more preferably from 90 to 10% by weight.
Is more preferred. Further, in order to maintain good transparency and weather resistance, the content is preferably 90 to 40% by weight, more preferably 90 to 60% by weight, and still more preferably 90 to 70% by weight in all monomer components. % Is good.

In the present invention, an unsaturated monocarboxylic acid (a1 ') may be used in combination as the (meth) acrylate monomer (a1). By using an unsaturated monocarboxylic acid (a1 ′) in combination, a thermoplastic resin (A) having a lactone ring structure and a glutaric anhydride ring structure introduced therein can be obtained, and the heat resistance and mechanical strength can be further improved. It is preferable because it can be performed. Examples of the unsaturated monocarboxylic acid (a1 ′) include, but are not particularly limited to, (meth) acrylic acid, crotonic acid, and α-substituted acrylic acid monomers that are derivatives thereof. Preferred is (meth) acrylic acid, and more preferred is methacrylic acid from the viewpoint of heat resistance. Further, the ester group derived from the (meth) acrylate monomer (a1) in the polymer (a) may have a structure equivalent to that of the unsaturated carboxylic acid (a1 ′) depending on conditions such as heating. Further, the carboxyl group of the unsaturated carboxylic acid (a1 ′) may have a salt structure such as a metal salt such as a sodium salt, as long as it does not hinder the cyclization condensation reaction described below. The proportion of the unsaturated monocarboxylic acid (a1 ′) in the monomer component is not particularly limited, and may be appropriately set within a range that does not impair the effects of the present invention.

The vinyl monomer (a2) having the structural unit represented by the general formula (2) includes, for example, a derivative of 2- (hydroxyalkyl) acrylic acid.
Specifically, a 2- (hydroxymethyl) acrylate monomer is preferably exemplified. More specifically,
For example, methyl 2- (hydroxymethyl) acrylate,
Ethyl 2- (hydroxymethyl) acrylate, isopropyl 2- (hydroxymethyl) acrylate, normal butyl 2- (hydroxymethyl) acrylate, t-butyl 2- (hydroxymethyl) acrylate, and the like,
Of these, methyl 2- (hydroxymethyl) acrylate and ethyl 2- (hydroxymethyl) acrylate are particularly preferred. Furthermore, methyl 2- (hydroxymethyl) acrylate is most preferable because it has a high effect of improving surface hardness, hot water resistance or solvent resistance. These may be used alone or in combination of two or more.

The proportion of the vinyl monomer (a2) having the structural unit represented by the general formula (2) in the monomer component is not particularly limited, but is 5 to 50% by weight. Is preferred. More preferably, it is 10 to 40% by weight, more preferably 15 to 35% by weight. When the proportion of the vinyl monomer (a2) is less than the above range, the amount of the ring structure is reduced, so that the surface hardness of the laminate may be reduced, and the hot water resistance and the solvent resistance may be reduced. Also,
The heat resistance of the laminate may be reduced. On the other hand, when it is larger than the above range, a cross-linking reaction occurs when the lactone ring structure is formed, so that gelation is likely to occur, the fluidity is reduced, and the melt molding may be difficult. Further, since unreacted hydroxyl groups are likely to remain, when the obtained thermoplastic resin (A) is molded, a condensation reaction further proceeds to generate volatile substances, and foams and silver streaks (surfaces) are formed on the laminate. Silver stripe pattern).

As the monomer component for obtaining the polymer (a), the above-mentioned (a) may be used as long as the effects of the present invention are not impaired.
It is also possible to use polymerizable monomers other than 1) and (a2). For example, styrene, vinyl toluene, α-
Examples include methylstyrene, acrylonitrile, methyl vinyl ketone, ethylene, propylene, vinyl acetate and the like. These may be used alone or in combination of two or more. When the above polymerizable monomers are used in combination as the monomer components for obtaining the polymer (a), the content of these monomers is preferably 0 to 30% by weight or less in the monomer components. Preferably, it is preferably 0 to 20% by weight or less, more preferably 0 to 10% by weight or less. When used in a predetermined amount or more in terms of physical properties and the like, good physical properties derived from the (meth) acrylate monomer, such as weather resistance, surface gloss, and transparency, may be impaired.

The method of the polymerization reaction when the monomer component is polymerized to obtain the polymer (a) is not particularly limited, but solution polymerization or bulk polymerization is preferred. As shown in EP 1 008 606, in the method of subjecting the polymer (a) to a cyclocondensation reaction to obtain a thermoplastic resin (A), it is preferable to perform a heat treatment in a solution. Polymerization is particularly preferred. The polymerization temperature,
The polymerization time varies depending on the type, ratio, and the like of the monomer components used, but is preferably a polymerization temperature of 50 to 150 ° C and a polymerization time of 0.5 to 20 hours, and more preferably a polymerization temperature of 80 to 140 ° C. The polymerization time is preferably 1 to 20 hours. The solvent that can be used in the polymerization reaction for obtaining the polymer (a) is not particularly limited, and for example, a solvent that is used in a normal radical polymerization reaction can be used. For example, toluene, xylene, Aromatic hydrocarbons such as ethylbenzene; ketones such as methyl ethyl ketone and methyl isobutyl ketone; chloroform, DMSO and tetrahydrofuran;
In particular, if the boiling point of the solvent to be used is too high, the residual volatile matter in the thermoplastic resin (A) increases, so that the polymer (a) can be dissolved at the processing temperature, and the boiling point is 50 to 200.
C is preferable, and for example, aromatic hydrocarbons such as toluene and ketones such as methyl ethyl ketone and methyl isobutyl ketone are more preferable. The amount of the solvent is 5 to 90% by weight, preferably 10 to 80% by weight, more preferably 30 to 75% by weight of the total amount. If the amount is less than 5% by weight, the viscosity of the polymer (a) becomes high, making it difficult to handle. On the other hand, if it exceeds 90% by weight, the solvent to be volatilized is too large and the productivity is reduced.

At the time of the polymerization reaction, an initiator may be added as required. The initiator is not particularly limited,
For example, cumene hydroperoxide, diisopropylbenzene hydroperoxide, di-t-butyl peroxide, lauroyl peroxide, benzoyl peroxide, t-butylperoxyisopropyl carbonate, t-amylperoxy-2-ethylhexanoate, etc. Organic peroxides; azo compounds such as 2,2'-azobis (isobutyronitrile), 1,1'-azobis (cyclohexanecarbonitrile), and 2,2'-azobis (2,4-dimethylvaleronitrile) ; These may be used alone or in combination of two or more. The amount of the initiator used may be appropriately set according to the combination of the monomers used and the reaction conditions.
There is no particular limitation.

The molecular weight of the polymer (a) obtained as described above is not particularly limited, but the weight average molecular weight (MW) measured by gel permeation chromatography (GPC) is 1,000. ~ 1,000,000
It is preferably 0. More preferably 5,000-
500,000, more preferably 50,000
３００300,000. If the Mw is lower than the above range, the mechanical strength of the thermoplastic resin (A) having a ring structure decreases, and the thermoplastic resin (A) becomes brittle. On the other hand, if it is higher than the above range, the fluidity is reduced and molding becomes difficult.

The thermoplastic resin (A) comprises the polymer (a)
To form a ring structure by a cyclocondensation reaction. The cyclization condensation reaction is a reaction in which a hydroxyl group and an ester group (or a carboxyl group) present in the molecular chain of the polymer (a) are cyclized and condensed to generate a lactone ring structure by heating. Alcohol and water are by-produced by cyclocondensation. By forming the ring structure in the molecular chain of the polymer (in the main skeleton of the polymer), high heat resistance is imparted and high surface hardness, hot water resistance and solvent resistance are imparted. A thermoplastic resin (A) having a lactone ring structure by cyclocondensation of the polymer (a)
For example, 1) a method of subjecting the polymer (a) to a cyclocondensation reaction by heating under reduced pressure with an extruder (Polym. Prepr., 8, 1, 576 (196)
7) 2) A method in which the cyclization condensation reaction of the polymer (a) is carried out in the presence of a solvent, and devolatilization is performed at the same time as the cyclization condensation reaction. 3) Using a specific organic phosphorus compound as a catalyst Use
A method of subjecting the polymer (a) to cyclocondensation (EP 10)
No. 08606). Of course, the present invention is not limited to these, and a plurality of methods among the above methods 1) to 3) may be employed. In particular, the reaction rate of the cyclocondensation reaction is high, bubbles and silver streaks can be suppressed from entering the laminate, and a decrease in mechanical strength due to a decrease in molecular weight during devolatilization can be suppressed. And the method using 3) is preferable.

The thermoplastic resin (A) in the present invention has a weight average molecular weight of 1,000 to 1,000,000, more preferably 5,000 to 500,000, and most preferably 50,000 to 300,000. Preferably, there is. If the weight average molecular weight is lower than the above range, surface hardness,
Not only does hot water resistance or solvent resistance decrease,
There is a problem that the mechanical strength is reduced and the material is apt to become brittle. On the other hand, if it is higher than the above range, the fluidity is reduced and molding becomes difficult, which is not preferable.

The thermoplastic resin (A) in the present invention has a glass transition temperature (Tg) of preferably 115 ° C. or more, more preferably 125 ° C. or more, and most preferably 130 ° C. or more. When the glass transition temperature is lower than 115 ° C., the hot water resistance decreases.

In the dynamic TG measurement of the thermoplastic resin (A) in the present invention, the weight reduction rate between 150 and 300 ° C. is preferably 1.0% or less, more preferably 0.5% or less, and even more preferably. Preferably it is 0.3% or less.

The thermoplastic resin (A) in the present invention has a lactone ring structure. The ratio of the lactone ring structure, which is determined from the weight loss between 150 and 300 ° C. in dynamic TG measurement, is as follows: The lactone ring structure is preferably 5 to 50% by weight, more preferably 10 to 40% by weight, and most preferably 10 to 30% by weight.
It is. In addition, the ratio occupied by the lactone ring structure can be specifically calculated by a method described later in Examples.
The thermoplastic resin (A) having a lactone ring structure according to the present invention is itself excellent in weather resistance, but when used outdoors, the thermoplastic resin (A) having a lactone ring structure according to the present invention may be used. It is preferable that the layer as a main component has an ultraviolet absorbing function. Specifically, the layer mainly containing the thermoplastic resin (A) having a lactone ring structure of the present invention,
It is preferable to have ultraviolet absorption and / or ultraviolet stability. Examples of the method include a method using an ultraviolet absorbing monomer and / or an ultraviolet stable monomer as a monomer component when producing the thermoplastic resin (A) having the lactone ring structure, and a method using an ultraviolet absorbing agent. And / or an ultraviolet stabilizer is blended with the thermoplastic resin (A) having the lactone ring structure. In addition, these methods may be used in combination, as long as the physical properties of the layer mainly containing the thermoplastic resin (A) having a lactone ring structure of the present invention are not affected. In order to maintain the ultraviolet absorbing function, it is preferable to use an ultraviolet absorbing monomer and an ultraviolet stable monomer in combination, or to use an ultraviolet absorber and an ultraviolet stabilizer in combination. Further, an ultraviolet absorbing monomer and / or
Alternatively, it is also preferable to use an ultraviolet absorber and / or an ultraviolet stabilizer in combination with the ultraviolet stable monomer.

Examples of the type of the above-mentioned UV-absorbing monomer include a benzotriazole compound, a benzophenone compound or a triazine compound and an acrylic monomer having a polymerizable unsaturated group. Examples of the benzotriazole-based compound include 2- [2′-hydroxy-5 ′-(meth) acryloyloxymethylphenyl] -2H-benzotriazole and 2- [2′-hydroxy-5 ′-(meth) acryloyloxyethyl Phenyl] -2H-benzotriazole, 2- [2'-hydroxy-5 '-(meth) acryloyloxypropylphenyl] -2H-benzotriazole, 2- [2'-hydroxy-5'-(meth) acryloyloxyhexyl Phenyl] -2H-benzotriazole, 2- [2'-hydroxy-3'-tert-butyl-5 '-(meth) acryloyloxyethylphenyl] -2H-benzotriazole, 2- [2'-hydroxy-5' − (Β- (meta)
Acryloyloxyethoxy) -3′-tert-butylphenyl] -5-tert-butyl-2H-benzotriazole and the like. As the benzophenone-based compound, for example, 2-hydroxy-4-
[2- (meth) acryloyloxy] ethoxybenzophenone, 2-hydroxy-4- [2- (meth) acryloyloxy] butoxybenzophenone, 2,2′-dihydroxy-4- [2- (meth) acryloyloxy] ethoxybenzophenone , 2-hydroxy-4- [2- (meth) acryloyloxy] ethoxy-4 '-(2-hydroxyethoxy)
Benzophenone or the like can be used. Further, as the triazine-based compound, for example, 4-diphenyl-6
-[2-hydroxy-4- (2-acryloyloxyethoxy)]-s-triazine, 2,4-bis (2-methylphenyl) -6- [2-hydroxy-4- (2-acryloyloxyethoxy)] -S-triazine, 2,4-bis
(2-methoxyphenyl) -6- [2-hydroxy-4-
(2-acryloyloxyethoxy)]-s-triazine and the like can be used. When such an ultraviolet absorbing monomer is used, 0.1 to 25% by weight of the total monomer is used.
Copolymerization is preferred, and more preferably 1-1.
Preferably, 5% by weight is copolymerized. If the content is small, the contribution of improving the weather resistance is low, and if the content is too large, the hot water resistance and the solvent resistance may be reduced, or yellowing may be caused.

As the UV-stable monomer, a hindered amine compound having a polymerizable unsaturated group bonded thereto can be used, and specific examples thereof include 4- (meth) acryloyloxy-2,2,2. 6,6-tetramethylpiperidine, 4- (meth) acryloylamino-2,2,
6,6-tetramethylpiperidine, 4- (meth) acryloyloxy-1,2,2,6,6-pentamethylpiperidine, 4- (meth) acryloylamino-1,2,2
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,
1- (meth) acryloyl-4- (meth) acryloylamino-2,2,6,6-tetramethylpiperidine, 1
-(Meth) acryloyl-4-cyano-4- (meth) acryloylamino-2,2,6,6-tetramethylpiperidine, 1-crotonoyl-4-crotonoyloxy-
2,2,6,6-tetramethylpiperidine and the like. When such a UV-stable monomer is used, it is preferably copolymerized at 0.1 to 25% by weight, more preferably at 1 to 15% by weight, based on all monomers. . If the content is small, the contribution of improving the weather resistance is low, and if the content is too large, the hot water resistance and the solvent resistance may be reduced, or yellowing may be caused.

Examples of the above-mentioned ultraviolet absorber include benzophenone compounds, salicate compounds, benzoate compounds, and triazole compounds.
Examples of the benzophenone-based compound include 2,4-dihydroxybenzophenone, 4-n-octyloxy-2-hydroxybenzophenone, and the like. Examples of the salicate-based compound include pt-butylphenyl salicate. Further, as the benzoate compound, 2,4-di-t-butylphenyl-3 ′, 5′-
Di-t-butyl-4'-hydroxybenzoate and the like. Further, as the triazole-based compound, 2- (5-methyl-2-hydroxyphenyl) benzotriazole, 2- [2-hydroxy-3,5-bis (α, α-dimethylbenzyl) phenyl] -2H- Benzotriazole and the like. These can be used alone or in combination of two or more. The blending amount of the ultraviolet absorbent is not particularly limited, but is preferably 0.01 to 25% by weight, more preferably 0.1 to 25% by weight in the layer mainly composed of the thermoplastic resin (A) having a lactone ring structure. 05 to 10% by weight. If the addition amount is too small, the contribution of improving the weather resistance is low, and if it is too large, the mechanical strength may decrease or yellowing may be caused.

In the layer containing the thermoplastic resin (A) as a main component in the present invention, in addition to the thermoplastic resin (A), various other additives may be added as needed within a range not to impair the effects of the present invention. Alternatively, another thermoplastic resin can be contained. However, even in that case, the proportion of the thermoplastic resin (A) in the layer containing the thermoplastic resin (A) in the present invention is preferably in the range of 50 to 100% by weight, and 7%.
The range of 5 to 100% by weight is more preferable, and 90 to 10% by weight is more preferable.
A range of 0% by weight is more preferred.

The above additives are not particularly limited,
In addition to the ultraviolet absorbers exemplified above, for example, antioxidants such as hindered phenol-based, phosphorus-based, and sulfur-based; reinforcing materials such as glass fiber; tris (dibromopropyl) phosphate, ethylene tetrabromide, Flame retardants such as antimony and zinc borate; antistatic agents such as anionic, cationic, nonionic and amphoteric surfactants; coloring agents such as inorganic pigments, organic pigments and dyes; The timing and amount of addition of these additives may be appropriately set as long as the effects of the present invention are not impaired.

The layer containing the thermoplastic resin (A) as a main component in the present invention may be usually formed by molding into a film or sheet. The molding is preferably performed at 150 to 350 ° C, more preferably at 200 to 300 ° C,
What is necessary is just to set suitably according to resin properties, such as heat resistance and fluidity, and it does not specifically limit. The molding method is not particularly limited, injection molding, extrusion molding, inflation molding,
Blow molding and the like can be mentioned. In the case of obtaining a film-like or sheet-like laminate, co-extrusion molding with a layer containing the thermoplastic resin (B) as a main component is preferable from the viewpoint of cost reduction, productivity improvement and moldability improvement.

<Layer mainly composed of thermoplastic resin (B)>
The thermoplastic resin (B) that can be used for the layer containing the thermoplastic resin (B) as a main component in the present invention is a pencil scratch test value (measured according to JIS-K 5400) of less than H and an Izod impact Strength (measured according to ASTM-D-256, notched, thickness 3.2 mm) of 10 kJ
Is not particularly limited as long as the thermoplastic resin is at least / m ² , specifically, a polycarbonate resin, a rubber-reinforced styrene resin, a vinyl chloride resin, a styrene resin,
Examples thereof include S (acrylonitrile styrene) resin, polyester resin, polyolefin resin, and polyamide resin, and one or more of these can be used.
More preferably, it is a thermoplastic resin comprising at least one selected from a polycarbonate resin, a rubber-reinforced styrene resin and a vinyl chloride resin. The above-mentioned thermoplastic resin is more preferable, and the pencil scratch test value (JIS
-K 5400) is a thermoplastic resin having an HB or lower, more preferably a B or lower, more preferably 2B or lower. Further, preferred ranges of Izod impact strength of the thermoplastic resin, 15 kJ / ^{m 2} or more, more preferably 20 kJ / ^{m 2} or more, more preferably 30kJ
/ M ² or more.

The term “main component” means that the content of the thermoplastic resin (B) is 50% when the layer formed of the thermoplastic resin (B) in the present invention is 100% by weight. It is in the range of -100% by weight. More preferably, it is in the range of 70-100% by weight, more preferably 80-100% by weight, and even more preferably 90-100% by weight.

Specific examples of the rubber-reinforced styrene resin include ABS (acrylonitrile butadiene rubber-styrene) resin, AES (acrylonitrile ethylene / propylene rubber-styrene) resin, AC
S (acrylonitrile chlorinated polyethylene-styrene) resin, AAS (acrylonitrile acrylic rubber-styrene) resin, and the like can be used, and one or more of these can be used.

Further, among these, the thermoplastic resin (A)
At least one resin selected from the group consisting of a polycarbonate resin, a rubber-reinforced styrenic resin, an AS resin and a vinyl chloride resin is preferred from the viewpoint of adhesion to a layer containing as a main component. Furthermore, polycarbonate resin, ABS resin,
At least one resin selected from vinyl chloride resins is preferred. Also, for example, polycarbonate resin and ABS
Resins may be blended. In order to obtain a transparent laminate, polycarbonate resin, transparent AB
The choice of S resin is preferred.

In the layer containing the thermoplastic resin (B) as a main component in the present invention, various additives and other additives described in the description of the layer containing the thermoplastic resin (A) as a main component may be used, if necessary. A thermoplastic resin may be blended. However, even in such a case, it is preferable that the components are blended so as to have an amount meaning the main component as described above.

The thermoplastic resin (B) may contain various additives as necessary. Examples of the additive include, but are not limited to, hindered phenol-based, phosphorus-based, and sulfur-based antioxidants; reinforcing materials such as glass fibers; phenyl salicylate, and 2 (2'-hydroxy-5-). Methylphenyl) benzotriazole, 2
UV absorbers such as hydroxybenzophenone; tris (dibromopropyl) phosphate, ethylene tetrabromide,
Flame retardants such as antimony oxide and zinc borate; antistatic agents such as anionic, cationic, nonionic and amphoteric surfactants; and colorants such as inorganic pigments, organic pigments and dyes. The timing and amount of addition of these additives may be appropriately set as long as the effects of the present invention are not impaired.

The layer containing the thermoplastic resin (B) as the main component in the present invention may be usually formed by molding into a film or sheet. The molding is preferably performed at 150 to 350 ° C, more preferably at 200 to 300 ° C,
What is necessary is just to set suitably according to resin properties, such as heat resistance and fluidity, and it does not specifically limit. The molding method is not particularly limited, injection molding, extrusion molding, inflation molding,
Blow molding and the like can be mentioned. When a film-like or sheet-like laminate is obtained, it is preferable to co-extrude with a layer containing the thermoplastic resin (A) as a main component from the viewpoint of cost reduction, productivity improvement and moldability improvement.

The thermoplastic resin (B) according to the present invention is mainly composed of
The layer to be used is used as a foam sheet if necessary.
You can also. The density of the foam is 0.05 to 0.3 g /
cm ³Is preferred. Density is 0.05g / cm³Less than
, The rigidity becomes poor, while 0.3 g / cm³Over
If it is obtained, the sheet becomes hard and the formability decreases.

<Laminate> The laminate of the present invention has a lactone ring structure formed by a cyclocondensation reaction of a polymer having a hydroxyl group and an ester group in the molecular chain, and has a pencil scratch test value ( A layer mainly composed of a thermoplastic resin (A) whose H is not less than H) (measured according to JIS-K 5400),
A thermoplastic resin (B) having a pencil scratch test value of less than H and an Izod impact strength (measured according to ASTM-D-256, notched, thickness 3.2 mm) of 10 kJ / m ² or more is used. A layer containing the thermoplastic resin (A) as a main component and having a thickness of 10 μm to 50 μm;
It is a thermoplastic resin laminate characterized by being in the range of 00 μm.

More specifically, an acrylic thermoplastic resin (A) having a lactone ring structure formed by subjecting a polymer having a hydroxyl group and an ester group in a molecular chain to a cyclocondensation reaction as a main component. And a layer mainly composed of a thermoplastic resin (B) containing at least one kind of a polycarbonate resin, a rubber-reinforced styrene resin, and a vinyl chloride resin, and mainly composed of the thermoplastic resin (A). This is a thermoplastic resin laminate having a layer thickness of 10 to 5000 μm.

More specifically, the laminate of the present invention can be obtained by laminating a layer containing the thermoplastic resin (A) and a layer containing the thermoplastic resin (B). At this time, the ratio of the thickness of both layers is such that the thickness (A ′) of the layer made of the thermoplastic resin (A) / the thickness (B ′) of the layer made of the thermoplastic resin (B) = 1/99 to 50/5
It is important that it is zero. By setting the thickness of both layers within the above range, it is possible to achieve both weather resistance, surface gloss, resistance such as solvent resistance and hot water resistance, and mechanical strength and impact resistance.

In the present invention, the thermoplastic resin (A) layer having a lactone ring structure formed by a cyclocondensation reaction of the polymer having a hydroxyl group and an ester group in the molecular chain; The method for laminating the layer (B) is not particularly limited, and a general method can be employed. For example, a method in which at least one of them is a sheet or a film or a foam and is heated and pressed, a method in which an adhesive resin is applied in advance on at least one surface and then heated and pressed, and a die of an extruder is used. A co-extrusion molding method for obtaining a sheet or a sheet by laminating a resin of a layer mainly containing the thermoplastic resin (A) and a layer mainly containing the thermoplastic resin (B); After the resin of the layer mainly composed of the thermoplastic resin (A) is given a three-dimensional shape by vacuum forming in advance, the resin of the layer mainly composed of the thermoplastic resin (B) is injected as a base material. An in-mold molding method for molding may be used. In order to reduce costs and improve productivity, a co-extrusion molding method and an in-mold molding method are preferred. In particular, when obtaining a sheet-like or film-like laminate, a co-extrusion molding method is preferable from the viewpoint of cost and productivity.

Further, in the above-mentioned method of in-mold molding, depending on the thickness of the layer mainly composed of the thermoplastic resin (A) and the layer mainly composed of the thermoplastic resin (B) of the desired laminate. It is also possible to apply a three-dimensional shape to the layer mainly composed of the thermoplastic resin (B) by vacuum forming in advance, and then in-mold the resin of the layer mainly composed of the thermoplastic resin (A). it can.

The laminate of the present invention may have the thermoplastic resin (A) layer on one surface of the layer containing the thermoplastic resin (B) as a main component, or may have the thermoplastic resin (A) layer on both sides. Is also good. When having a thermoplastic resin (A) layer on one side,
A laminate excellent in resistance to light rays such as ultraviolet rays from one direction, abrasion stress, solvents and hot water is obtained, and when a thermoplastic resin (A) layer is provided on both sides, ultraviolet rays from both directions can be obtained. A laminate having excellent resistance to light, abrasion stress, solvent and hot water can be obtained. That is, the laminate of the present invention comprises, as a main component, a thermoplastic resin (A) having a specific structure having a lactone ring structure formed by subjecting a polymer having a hydroxyl group and an ester group in a molecular chain to a cyclocondensation reaction. By the layer to be expressed, it is possible to develop weather resistance and high surface hardness, and also to exhibit resistance to hot water and a solvent, and the layer mainly composed of the thermoplastic resin (B) originally has Excellent mechanical strength and impact resistance can be maintained as a laminate structure. What is necessary is just to set the laminated form of the laminated body of this invention suitably according to a use.

The laminate of the present invention can be prepared in addition to a layer mainly composed of the thermoplastic resin (A) layer and a layer mainly composed of the above-mentioned specific thermoplastic resin (B). , A third layer. In this case, in order to exhibit the effects of the present invention, such as weather resistance, high surface hardness, and resistance to a solvent or hot water, a layer mainly composed of the thermoplastic resin (A) is disposed on at least one surface. is important. As the third layer, for example, a composite layer using a thermoplastic resin (A), a specific thermoplastic resin (B) or another thermoplastic resin, a colored layer thereof, or a reinforcing layer containing a filler or the like And the like. Further, a layer printed with a desired material may be provided at an arbitrary position. By having the printed layer, the laminate of the present invention can further retain its design. The printed layer may be on a part of the laminate of the present invention or on the front surface.
When it is a part, when the laminate of the present invention is a transparent laminate, it may be a printed layer or a colored layer for hiding the adhesive layer at the time of construction.

The laminate of the present invention is preferably in the form of a sheet because various shapes can be easily formed.
Of course, the present invention is not limited to this, and may be in the form of a cylinder or a container.

When the laminate of the present invention is used as a sheet, its thickness can be appropriately set depending on the purpose of use, for example, 0.25 mm to 5 cm for the entire sheet.
Is preferred. A more preferred thickness is from 0.5 mm to 4 cm. A more preferred thickness is from 0.8 mm to 3.0 cm. More preferably, it is 0.8 mm to 1 cm. When used in the form of a film, the thickness of the entire film is preferably 20 to 250 μm.

In the laminate of the present invention, for example, when a laminate having transparency is used, ASTM-D-1003 may be used.
80% or more of the total light transmittance measured by a method according to
It is more preferably at least 85%, most preferably at least 88%. The total light transmittance is a measure of transparency. If the total light transmittance is less than 80%, the transparency is reduced, and it may not be used for the originally intended use. Further, in the case of forming a laminate having the above transparency, the haze value measured by a method according to ASTM-D-1003 is 5% or less, preferably 3% or less, more preferably 1% or less. Preferably, there is. The haze value is a measure of transparency, and if it exceeds 5%, the transparency is reduced, and it may not be used for the originally intended use. In the laminate of the present invention, it is a preferred embodiment to have the above-described physical properties such as weather resistance, high surface hardness (scratch resistance), solvent resistance, and hot water in accordance with the transparency. . Further, since there is a layer mainly composed of the thermoplastic resin (B) of the laminate, a transparent laminate having further excellent strength physical properties such as impact strength is obtained, which is one of the preferable embodiments of the laminate of the present invention.

In the laminate of the present invention, when a layer mainly composed of the thermoplastic resin (A) is used as a surface layer, a pencil scratch test value (measured according to JIS-K 5400) is H or more. Is preferable, more preferably 2H or more, and most preferably 3H or more. If it is softer than H, it may be easily scratched, and the appearance may worsen. The pencil scratch test value can also be expressed as pencil hardness.

The laminate of the present invention has both weather resistance, high surface hardness (scratch resistance), resistance to solvents and hot water, and mechanical strength and impact resistance.
Carports, signboards, glazing materials for construction, glazing materials for various vehicles, interior parts for automobiles, soundproof walls, surface resin sheets for bathtubs, sheets for sanitary products such as washbasins, sheets for various household products, sheets for thermoforming, It can be suitably used for a sheet for thermoforming for the purpose of depainting.

[0061]

EXAMPLES Examples of the present invention will be described below as examples and comparative examples. Hereinafter, the present invention will be described more specifically with reference to Examples and Comparative Examples, but the present invention is not limited thereto. In addition,
In each of the following Examples and Comparative Examples, the description of “parts” indicates “parts by weight”.

Each analysis in the examples was performed as follows.

(Polymerization Reaction Rate, Polymer Composition Analysis) The reaction rate at the time of polymerization reaction and the content of specific monomer units in the polymer are determined by the amount of unreacted monomer in the obtained polymerization reaction mixture. Gas chromatography (Shimadzu Corporation, device name: GC
-14A).

(Dynamic TG) The obtained polymer (or polymer solution or pellet) is once dissolved or diluted in tetrahydrofuran, poured into an excessive amount of hexane or methanol, and reprecipitated. (1.33 hPa, 80 ° C, 3 hours or more)
By doing so, volatile components and the like were removed, and the obtained white solid resin was analyzed under the following conditions.

Measuring device: Thermo Plus2 TG-8120 Dynamic
TG (manufactured by Rigaku Co., Ltd.) Measurement conditions: sample amount: 5 to 10 mg, heating rate: 10
° C / min, atmosphere is nitrogen flow 200ml / mi
n, the method is a stepwise isothermal control method (control at a weight reduction rate of 0.005% / sec or less between 60 and 500 ° C) (dealcoholization reaction rate and ratio of lactone ring structure)
The dealcoholation reaction rate is based on the weight loss that occurs when all hydroxyl groups are de-alcoholized as methanol from the polymer composition obtained by polymerization. It was determined from the weight loss due to the dealcoholation reaction up to 300 ° C. before the decomposition started.

That is, in a dynamic TG measurement of a polymer having a lactone ring structure, 150 ° C. to 300 ° C.
The weight loss rate during the period up to the above is measured, and the obtained measured weight loss rate is defined as (X). On the other hand, from the composition of the polymer,
The theoretical weight loss rate when assuming that all of the hydroxyl groups contained in the polymer composition are involved in the formation of a lactone ring and become alcohol and dealcoholate (that is, 100% dealcoholization reaction occurs on the composition). (Y) is the weight loss rate calculated in this way. More specifically, the theoretical weight loss rate (Y) is, more specifically, the molar ratio of the raw material monomer having a structure (hydroxyl group) involved in the dealcoholation reaction in the polymer, that is, the raw material monomer in the polymer composition. It can be calculated from the content of the monomer. These values (X, Y) are substituted into the dealcohol calculation formula: 1− (measured weight loss rate (X) / theoretical weight loss rate (Y)), and the values are obtained. Rate is obtained. Then, assuming that the predetermined lactone cyclization has been performed by the dealcoholization reaction rate, the content (weight ratio) of the raw material monomer having the structure (hydroxyl group) involved in the lactone cyclization in the polymer composition, By multiplying by the dealcoholation reaction rate, the ratio of the lactone ring structure in the polymer can be calculated.

As an example, the ratio of the lactone ring structure in the polymer obtained in Reference Example 1 described below is calculated. When the theoretical weight loss rate (Y) of this polymer was determined, the molecular weight of methanol was 32, the molecular weight of methyl 2- (hydroxymethyl) acrylate was 116,
Polymer of methyl (hydroxymethyl) acrylate (A-
Since the content (weight ratio) in 1) is 20.1% by weight in terms of composition, (32/116) × 20.1 ≒ 5.54% by weight.
Becomes On the other hand, the weight loss rate (X) measured by dynamic TG measurement was 0.15% by weight. When these values are applied to the above-described alcohol removal calculation formula, 1- (0.1
5 / 5.54) ≒ 0.973, and the dealcoholization reaction rate is 97.3%. Then, assuming that the predetermined lactone cyclization has been performed by the amount corresponding to the dealcoholization reaction rate in the polymer, the content of methyl 2- (hydroxymethyl) acrylate in the polymer (20.1% by weight)
Is multiplied by the dealcoholation reaction rate (97.3% = 0.973), the ratio of the lactone ring structure in the polymer is 19.6 (20.1 x 0.973) wt%.

(Weight Average Molecular Weight) The weight average molecular weight of the polymer was determined by GPC (GPC system manufactured by Tosoh Corporation) in terms of polystyrene.

(Coloring degree YI of resin) Coloring degree YI of resin
Is prepared by dissolving a resin in chloroform, placing a 15% by weight solution in a quartz cell, and using a color difference meter (manufactured by Nippon Denshoku Industries Co., Ltd., device name: SZ- # 90) in accordance with JIS-K-7103, using transmitted light. It was measured.

(Thermal analysis of resin)
(Manufactured by Rigaku Corporation, device name: DSC-8230). In addition, the glass transition temperature (Tg) is ASTM-D
Determined by the midpoint method according to -3418.

(Confirmation of Lactone Ring Structure in Resin) Whether a lactone ring structure is present in the resin skeleton was confirmed by infrared absorption spectrum and ¹³ C-NMR. Incidentally, infrared absorption spectrum, using FTS-45 infrared spectrophotometer (manufactured by ^{BIO-RAD), 13 C-} NMR is
FT-NMR unity plus400 (Vari
measurement).

(Transparency of laminate) As an index of transparency,
The total light transmittance of the obtained laminate (thickness: 3.1 mm)
According to ASTM D1003, measurement was performed using a turbidimeter (manufactured by Nippon Denshoku Industries Co., Ltd., device name: NDH-1001DP).

(Hot water resistance of laminate) 5 cm × 5
cm, and the surface of the layer mainly composed of the thermoplastic resin (A) was brought into contact with hot water at 90 ° C., and after standing for 100 hours, its appearance was observed. (Solvent resistance of the laminate) The laminate was cut into 5 cm x 5 cm, and the surface of the layer mainly composed of the thermoplastic resin (A) was brought into contact with isopropyl alcohol (IPA) or xylene. The appearance was observed. (Scratch Resistance of Laminate) The layer mainly composed of the thermoplastic resin (A) was used as a surface layer, and the abrasion resistance of the laminate was measured according to JIS-K.
-5400, pencil scratch tester (JIS-K-5
Using 401), a pencil scratch test value (pencil hardness) was measured. (Weather resistance of laminate) According to JIS-A-1415, 60
An accelerated exposure test was performed at ° C. Specifically, a layer containing the thermoplastic resin (A) as a main component is irradiated with a sunshine carbon arc lamp to measure the time-dependent change in the yellowing degree (YI) of the test piece, and the difference from the initial value (YI) is measured. ΔYI).

REFERENCE EXAMPLE 1 10 parts of methyl 2- (hydroxymethyl) acrylate, 40 parts of methyl methacrylate, and 50 parts of toluene were placed in a 30 L reactor equipped with a stirrer, a temperature sensor, a cooling pipe, and a nitrogen inlet pipe. And heated to 100 ° C. while passing nitrogen. At the reflux, 0.15 parts of tertiary butyl peroxyisopropyl carbonate as an initiator was added, and the mixture was refluxed (100 to 110).
℃), and aging was performed for 5 hours. The polymerization reaction rate was 95.0%, and the content (weight ratio) of methyl 2- (hydroxymethyl) acrylate in the polymer was 20.
1%. The weight average molecular weight of this polymer is 1
It was 50,000.

3 parts per 100 parts of the obtained polymer component
7.5 parts of methyl isobutyl ketone and 0.3 part of a stearyl phosphate / distearyl phosphate mixture based on 100 parts of the polymer solution (“Phoslex A” manufactured by Sakai Chemical Co., Ltd.)
-18 "), and while refluxing nitrogen (95-1)
(00 ° C.) for 5 hours. A part of the obtained reaction solution was taken out, and dynamic TG was measured. As a result, a weight loss rate of 0.70% was detected.

Next, the obtained polymer solution was subjected to a barrel temperature of 250 ° C., a rotation speed of 100 rpm, and a degree of vacuum of 13.3 to 4
00 hPa, a vent type screw twin screw extruder with one rear vent and one forevent (diameter = 29.75)
mm, L / D = 30) at a processing rate of 2.0 kg / hour in terms of the amount of resin, cyclized condensation reaction and devolatilization in the extruder, and extruded to obtain a transparent thermoplastic resin ( A
-1) Pellets were obtained.

The color YI of the pellet was 0.7. When dynamic TG was measured on the obtained pellet, a weight reduction rate of 0.15% was detected. The weight average molecular weight of the pellet was 165,0
00 and the glass transition temperature was 134 ° C. About this pellet, infrared absorption spectrum analysis,
^{1 3} was subjected to ^C-NMR spectrum analysis, that there is a lactone ring structure in the resin skeleton were confirmed.

REFERENCE EXAMPLE 2 Immediately before performing the cyclization condensation reaction and devolatilization in the extruder, 100 parts of the polymer was used as an ultraviolet absorber as 2- (5-methyl-2-hydroxyphenyl) benzotriazole. A transparent thermoplastic resin (A) in the same manner as in Reference Example 1 except that 0.1 part by weight of “Tinuvin P” manufactured by Ciba Specialty Chemicals was added.
-2) A pellet was obtained. The coloring degree of the pellet is Y
I was 0.8. When dynamic TG measurement was performed on the obtained pellet, a weight reduction rate of 0.15% was detected. The weight average molecular weight of the pellet was 165,000, and the glass transition temperature was 134 ° C. When infrared absorption spectrum analysis and ¹³ C-NMR spectrum analysis were performed on the pellet, it was confirmed that a lactone ring structure was present in the skeleton of the resin.

Example 1 As a thermoplastic resin (B),
Pencil hardness 2B, Izod impact strength 83 kJ / m ²
Using a polycarbonate resin (“Panlite L-1225” manufactured by Teijin Chemicals), together with the thermoplastic resin (A-1) obtained in Reference Example 1, under the following conditions,
A laminated sheet having a thickness of 3 mm of the polycarbonate resin layer and 0.1 mm of the thermoplastic resin (A-1) layer was obtained. Table 1 shows the results of surface hardness, weather resistance test, solvent resistance and hot water resistance of this sheet. The total light transmittance of this sheet was 88%.

[Conditions of Extruder] Polycarbonate resin side: screw diameter φ50 mm, barrel temperature 270 ° C. Thermoplastic resin (A-1) side: screw diameter φ20 mm,
Barrel temperature 260 ° C. Die: Temperature 260 ° C., width 1000 mm Shiny three-roll temperature: 125 ° C. for first roll, 142 ° C. for second roll, 118 ° C. for third roll Picking speed: 1.5 m / min [Example 2] Heat Instead of the plastic resin (A-1), (A
Except for using -2), a laminated sheet was obtained in the same manner as in Example 1. Table 1 shows the evaluation results of this sheet. In addition,
The total light transmittance of this sheet was 88%.

Comparative Example 1 Table 1 shows the evaluation results of the single sheet (thickness: 3.1 mm) of the polycarbonate resin used in Example 1.

Comparative Example 2 Instead of the thermoplastic resin (A-1), a PMMA resin (“SUMIPEX EX” manufactured by Sumitomo Chemical Co., Ltd.) was used as the methacrylic resin, and the barrel temperature of the extruder on the PMMA side was set to 250 ° C. A laminated sheet was obtained in the same manner as in Example 1 except for the above. Table 1 shows the results of the evaluation so that the PMMA side becomes the surface layer. The delta YI in the weather resistance properties in the table is ΔYI.

[0083]

[Table 1] Example 3 A thermoplastic resin (B) having a pencil hardness of 2
B, ABS with Izod impact strength of 59 kJ / m ²
Reference Example 1 using resin (Toray “Toyolac 600”)
Coextruded together with the thermoplastic resin (A-1) obtained in the above, and the ABS resin layer was 3 mm thick, and the thermoplastic resin (A-
1) A laminated sheet having a layer thickness of 0.1 mm was obtained. In the case of co-extrusion molding, the barrel temperature of the extruder on the ABS resin side was set to 250 ° C, the barrel temperature of the extruder on the thermoplastic resin (A-1) side was set to 250 ° C, and the temperature of the die was set to 250 ° C. Molded. Table 2 shows the evaluation results of the obtained laminated sheet. Example 4 Instead of the thermoplastic resin (A-1), (A-
A laminated sheet was obtained in the same manner as in Example 3 except that 2) was used. Table 2 shows the evaluation results of this sheet.

Comparative Example 3 Table 2 shows the evaluation results of the ABS resin alone sheet (thickness: 3.1 mm) used in Example 3. Comparative Example 4 A laminated sheet was obtained in the same manner as in Example 3 except that the PMMA resin used in Comparative Example 2 was used instead of the thermoplastic resin (A-1). Table 2 shows the results of the evaluation so that the PMMA side becomes the surface layer. The delta YI in the weather resistance properties in the table is ΔYI.

[0085]

[Table 2]

[0086]

According to the present invention, a thermoplastic resin having excellent weather resistance and surface hardness (scratch resistance), excellent resistance to hot water and solvents, and excellent mechanical strength and impact resistance. A resin laminate can be provided. The following configuration is adopted for that purpose.

The present invention has a lactone ring structure formed by a cyclocondensation reaction of a polymer having a hydroxyl group and an ester group in a molecular chain, and has a pencil scratch test value (JI
A layer whose main component is a thermoplastic resin (A) whose S-K 5400 is H or more, a pencil scratch test value of less than H, and an Izod impact strength (ASTM-
Measurement according to D-256, with notch, thickness 3.2m
m) has a layer mainly composed of the thermoplastic resin (B) having a value of 10 kJ / m ² or more, and the thickness of the layer mainly composed of the thermoplastic resin (A) is in a range of 10 μm to 5000 μm. A thermoplastic resin laminate characterized by the following. More preferably, the thermoplastic resin (B) is at least one type of thermoplastic resin selected from a polycarbonate resin, a rubber-reinforced styrene resin, and a vinyl chloride resin. Body.

Similarly, the present invention has a lactone ring structure formed by a cyclocondensation reaction of a polymer having a hydroxyl group and an ester group in a molecular chain.
A layer mainly composed of an acrylic thermoplastic resin (A),
A layer mainly composed of at least one thermoplastic resin (B) selected from a polycarbonate resin, a rubber-reinforced styrene resin and a vinyl chloride resin, and a layer mainly composed of the thermoplastic resin (A) Has a thickness in the range of 10 μm to 5000 μm.

Continued on front page F-term (reference) 4F100 AK01B AK12B AK25A AK25K AK45B AL06B AN02B BA02 BA10A BA10B BA15 EH20 GB32 GB71 JA20A JB16A JB16B JD14 JD14A JK01 JK10 JK10B JK12A JK13BJP04 AL08B

Claims (7)

[Claims] 1. A compound having a hydroxyl group and an ester group in a molecular chain.
Formed by a cyclocondensation reaction of a polymer
It has a lactone ring structure and has a pencil scratch test value (JIS-K
 Thermoplastic resin whose H value is equal to or greater than H
(A) as a main component and a pencil scratch test value of H
Full and Izod impact strength (ASTM-D-2
(Measurement according to 56, notch, thickness 3.2mm) is 1
0kJ / m ²The above-mentioned thermoplastic resin (B) as a main component
Having a layer to be formed, wherein the main component is the thermoplastic resin (A).
That the thickness of the layer is in the range of 10 μm to 5000 μm
Characteristic thermoplastic resin laminate. 2. A (meth) acrylic thermoplastic resin (A) having a lactone ring structure formed by subjecting a polymer having a hydroxyl group and an ester group in a molecular chain to a cyclocondensation reaction as a main component. And a thermoplastic resin (B) comprising at least one selected from a polycarbonate resin, a rubber-reinforced styrene resin and a vinyl chloride resin
Wherein the thickness of the layer containing the thermoplastic resin (A) as a main component is in the range of 10 μm to 5000 μm. 3. The thermoplastic resin laminate according to claim 1, wherein the lactone ring structure of the thermoplastic resin (A) is a structure represented by the following general formula (1). . Embedded image (In the formula (1), R ¹ , R ² and R ³ each independently represent a hydrogen atom or an organic residue having 1 to 20 carbon atoms. The organic residue may include an oxygen atom. .) 4. The thermoplastic resin laminate according to claim 1, wherein the thermoplastic resin (A) contains a methyl methacrylate monomer unit. 5. A sheet-like sheet wherein the ratio of the thickness of the layer mainly composed of the thermoplastic resin (A) to the thickness of the layer mainly composed of the thermoplastic resin (B) is 1/99 to 50/50. The thermoplastic resin laminate according to any one of claims 1 to 4, which is in the form of: 6. The thermoplastic resin laminate according to claim 1, wherein the thermoplastic resin (A) has an ultraviolet absorbing function. 7. The method according to claim 1, wherein the layer mainly composed of the thermoplastic resin (A) and the layer mainly composed of the thermoplastic resin (B) are co-extruded. 4. The thermoplastic resin laminate according to item 1.