JP2002120326A - Transparent thermoplastic resin laminate - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a transparent thermoplastic resin laminate which is excellent in resistance to hot water and a solvent, mechanical strength, and impact resistance. SOLUTION: In the laminate including a layer containing a thermoplastic resin (A) having lactone ring structure which is prepared by the cyclic condensation reaction of a polymer having hydroxyl groups and ester groups in a molecular chain and a layer containing a methacrylic resin (B) prepared by polymerizing a monomer composition containing at least 85 wt.% of methyl methacrylate, the ratio of the thickness (A') of the layer containing the resin (A) to the thickness (B') of the layer containing the resin (B) is expressed by (A')/(B')=1/99-50/50.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a transparent thermoplastic resin laminate having excellent resistance to hot water and solvents, and excellent mechanical strength and impact resistance.

[0002]

2. Description of the Related Art Methacrylic resins are excellent in transparency, surface gloss and weather resistance, and are well-balanced in mechanical strength, molding workability and surface hardness. It is widely used for transparent materials in various industrial parts and miscellaneous goods, and for optical-related applications. However, the glass transition temperature (Tg) of the methacrylic resin is 10
Since it is around 0 ° C., it has been difficult to use it in a field where heat resistance is required. In addition, methacrylic resins have no resistance to alcohols and hydrocarbon solvents, and have poor resistance to hot water. Therefore, when they are immersed in these for a long time, they have the problem of whitening or deformation.

[0003]

As a transparent heat-resistant resin that solves this problem, the present inventors have formed a polymer having a hydroxyl group and an ester group in a molecular chain by a cyclocondensation reaction. A thermoplastic resin having a lactone ring structure was proposed in EP 1 008 606. But,
This thermoplastic resin has improved heat resistance and excellent solvent resistance and hot water resistance, but in applications where high impact resistance is required, the same use as conventional methacrylic resins may be restricted. there were. Therefore, an object of the present invention is to provide a transparent thermoplastic resin laminate excellent in resistance to hot water and a solvent, and excellent in mechanical strength and impact resistance.

[0004]

Means for Solving the Problems The present inventors have conducted intensive studies to solve these problems, and as a result, a thermoplastic resin (A) having a lactone ring structure and a methacrylic resin (B) have been developed. It has been found that by laminating at a specific ratio thickness, resistance such as hot water resistance and solvent resistance, and mechanical strength and impact resistance can be simultaneously satisfied, and the present invention has been completed. That is, the transparent thermoplastic resin laminate of the present invention contains a 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. And a layer containing a methacrylic resin (B) obtained by polymerizing a monomer component containing 85% by weight or more of methyl methacrylate, and the thickness of the layer containing the thermoplastic resin (A) ( A ′) and the thickness (B ′) of the layer containing the methacrylic resin (B) are (A ′) / (B ′) = 1 /
99 to 50/50.

[0005]

BEST MODE FOR CARRYING OUT THE INVENTION The transparent thermoplastic resin 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 a molecular chain. A layer containing (A) and a layer containing methacrylic resin (B) obtained by polymerizing a monomer component containing 85% by weight or more of methyl methacrylate are laminated. Hereinafter, each layer will be described. <Layer containing thermoplastic resin (A)> The thermoplastic resin (A) has a lactone ring structure formed by a cyclocondensation reaction of a polymer (a) having a hydroxyl group and an ester group in a molecular chain. Is a thermoplastic resin. Specifically, the lactone ring structure is preferably a structure represented by the following general formula (1).

[0006]

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(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 contains 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-based polymer. Preferable examples include a polymer obtained by polymerizing a monomer component including a monomer (a1) and a vinyl monomer (a2) having a structural unit represented by the following general formula (2).

[0008]

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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, in terms of heat resistance and transparency, methyl methacrylate and methyl acrylate are preferable, and methyl methacrylate is more preferable. Further, a (meth) acrylate having a cyclohexyl group is preferable in that the water absorption of the polymer (a) can be reduced and weather resistance can be imparted to the polymer (a). Further, a (meth) acrylate having an aromatic group is preferable because an aromatic ring can further improve heat resistance.

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, as the (meth) acrylate monomer (a1), an unsaturated monocarboxylic acid (a1 ′) is used.
May be used in combination. 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. Unsaturated monocarboxylic acid (a
Examples of 1 ′) 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-based monomer (a1) in the polymer (a) may be an unsaturated carboxylic acid (a
The structure may be equivalent to 1 '). 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. In addition,
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, tertiary butyl 2- (hydroxymethyl) acrylate, etc. And methyl 2- (hydroxymethyl) acrylate and ethyl 2- (hydroxymethyl) acrylate. Furthermore, methyl 2- (hydroxymethyl) acrylate is most preferable because of its high heat resistance improving effect. 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 heat resistance is lowered and the solvent resistance is sometimes lowered. In addition, the surface hardness of the laminate may decrease. 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 a monomer component for obtaining the polymer (a), a polymerizable monomer other than the above (a1) and (a2) can be used depending on desired physical properties. For example,
Specific examples include a monomer represented by the following general formula (3), and specific examples include styrene, vinyl toluene, α-methylstyrene, acrylonitrile, methyl vinyl ketone, ethylene, propylene, and vinyl acetate. Among these, styrene and α-methylstyrene are particularly preferred from the viewpoint that a benzene ring structure can be introduced and the glass transition temperature can be improved. These may be used alone or in combination of two or more.

[0015]

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(In the formula (3), R ⁶ represents a hydrogen atom or a methyl group, X represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group, a —OAc group, a —CN group, a —CO—
R ⁷ represents a —CO—R ⁸ group; Ac represents an acetyl group; R ⁷ and R ⁸ represent a hydrogen atom or a carbon atom
Represents 20 organic residues. When the polymerizable monomer is used in combination as the monomer component for obtaining the polymer (a), the content of these monomers is preferably 30% by weight or less in the monomer component. The content is more preferably 20% by weight or less, further preferably 10% by weight or less. In terms of physical properties, etc., when used over a predetermined amount,
In some cases, physical properties such as transparency and heat resistance, which are good physical properties derived from the (meth) acrylate-based monomer, are impaired. Specifically, the amount of the polymerizable monomer is preferably in the range of 0 to 30% by weight in the monomer component, more preferably 0 to 30% by weight.
The content is preferably 20% by weight, more preferably 0 to 10% by weight.

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 0 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 10 hours.

The solvent that can be used in the polymerization reaction for obtaining the polymer (a) is not particularly limited. For example, a solvent used in a usual radical polymerization reaction can be used. , 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 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 2
The thing of 00 degreeC is preferable, for example, aromatic hydrocarbons, such as toluene, ketones, such as methyl ethyl ketone and methyl isobutyl ketone, etc. are more preferable. The amount of the solvent is 5 to 90% by weight of the total amount, preferably 10 to 80%.
%, More preferably 30 to 75% by weight. 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 and the like 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) is obtained by subjecting the polymer (a) to a cyclization condensation reaction to form a ring structure. 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.

The method for obtaining the thermoplastic resin (A) having a lactone ring structure by cyclizing and condensing the polymer (a) includes, for example, 1) the above-mentioned polymer (a) under reduced pressure using an extruder. Heating to effect a cyclization condensation reaction (Polym. P
repr. , 8,1,576 (1967), 2) the cyclocondensation reaction of the polymer (a) is carried out in the presence of a solvent, and
A method in which devolatilization is carried out at the same time as the cyclization condensation reaction; 3) a method using the above polymer (a)
(European Patent No. 1086606). 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) may contain various additives as required. 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 thermoplastic resin (A) in the present invention has a weight average molecular weight of 40,000 to 300,000, more preferably 80,000 to 200,000, and most preferably 100,000 to 200,000. Is preferred. When the weight average molecular weight is less than 40,000, there is a problem that the mechanical strength is reduced and the material tends to be brittle,
On the other hand, if it exceeds 300,000, the fluidity is lowered and molding becomes difficult, which is not preferable. The thermoplastic resin (A) in the present invention has a content of 5% in thermogravimetric analysis (TG).
The weight loss temperature is 330 ° C. or higher, more preferably 35 ° C.
It is preferably 0 ° C. or higher, most preferably 360 ° C. or higher. The 5% weight loss temperature is an index of thermal stability. If the temperature is less than 330 ° C., sufficient thermal stability cannot be exhibited.

The thermoplastic resin (A) in the present invention has a glass transition temperature (Tg) of preferably 115 ° C. or higher, more preferably 125 ° C. or higher, and even more preferably 13 ° C. or higher.
It is at least 5 ° C, most preferably at least 140 ° C. In the dynamic TG measurement of the thermoplastic resin (A) in the present invention, the weight loss rate between 150 and 300 ° C. is 1.0%.
Or less, more preferably 0.5% or less,
It is even more preferably 0.3% or less. The thermoplastic resin (A) in the present invention has a lactone ring structure, and the proportion of the lactone ring structure, which is determined from the weight loss between 150 and 300 ° C. in dynamic TG measurement, is the ratio of 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.

[0025] The residual volatile matter in the thermoplastic resin (A) in the present invention is preferably 1500 ppm or less, more preferably 1000 ppm or less. If more than this,
It causes coloring, foaming, and poor molding such as silver due to deterioration during molding. In the layer containing the thermoplastic resin (A) in the present invention, in addition to the thermoplastic resin (A), other thermoplastic resins may be contained as long as the effects of the present invention are not impaired. . When another thermoplastic resin is used in combination, the content of the other thermoplastic resin is 30% by weight based on the total thermoplastic resin obtained by combining the thermoplastic resin (A) and the other thermoplastic resin. It is preferably at most 20% by weight, more preferably at most 10% by weight. Specifically, the proportion of the thermoplastic resin (A) in the layer containing the thermoplastic resin (A) in the present invention is 70 to 1
The content is preferably in the range of 00% by weight, more preferably 80 to 1%.
The content is preferably 00% by weight, more preferably 90 to 100% by weight.

The layer containing the thermoplastic resin (A) in the present invention may be usually formed by molding the thermoplastic resin (A) into a film, a sheet or the like. Molding is 15
It is preferably performed at 0 to 350 ° C, more preferably at 20 ° C.
The temperature is 0 to 300 ° C., but may be appropriately set according to the properties of the resin such as heat resistance, and is not particularly limited. The molding method is not particularly limited, and examples include injection molding, blow molding, and extrusion molding. When the thermoplastic resin (A) is used as a sheet, the thickness is preferably 0.25 to 5 mm. When used in the form of a film, 10 to 250 μm
m is preferred.

<Layer Containing Methacrylic Resin (B)>
The methacrylic resin (B) is obtained by polymerizing a monomer component containing 85% by weight or more of methyl methacrylate. When the content of methyl methacrylate is less than 85% by weight, optical properties such as transparency are reduced, and mechanical strength is reduced. As the monomer component, for example, other (meth) acrylic acid esters may be contained in addition to methyl methacrylate. As the other (meth) acrylic acid ester, a (meth) acrylic acid ester having any one of an alkyl group having 2 to 18 carbon atoms, a cyclohexyl group, and a benzyl group is preferable. Methyl acrylate, ethyl (meth) acrylate, (meth)
Propyl acrylate, t-butyl (meth) acrylate,
Examples thereof include cyclohexyl (meth) acrylate and benzyl (meth) acrylate.

The monomer components may contain, for example, polyvalent (meth) acrylates in addition to methyl methacrylate. Specific examples of polyvalent (meth) acrylates include ethylene glycol di (meth) acrylate, diethylene glycol (meth) acrylate, divinylbenzene, diallyl phthalate, trimethylolpropane tri (meth) acrylate, and hexanediol di (meth) acrylate. Acrylate and the like. In the case where the polyvalent (meth) acrylates are used, the layer containing the methacrylic resin (B) in the present invention is partially cross-linked as long as the moldability as a thermoplastic resin is not hindered. It may contain a resin.

The monomer component may contain, for example, a monomer represented by the general formula (3) in addition to methyl methacrylate. Specific examples include styrene, vinyltoluene, α-methylstyrene, acrylonitrile, methyl vinyl ketone, ethylene, propylene, vinyl acetate and the like. As the monomer other than methyl methacrylate that can be contained as the monomer component, only one kind may be used, or two or more kinds may be appropriately used in combination. When these monomers are contained, the content is not particularly limited as long as the content is less than 15% by weight in the monomer components.

The methacrylic resin (B) may contain a rubbery polymer as required. As the rubbery polymer, polybutadiene rubber, styrene butadiene rubber,
Ethylene propylene rubber, acrylic rubber and the like can be mentioned, but it is preferable to use acrylic rubber from the viewpoint of transparency. As the methacrylic resin (B) containing a rubbery polymer, impact-resistant polymethyl methacrylate (PMMA) is preferably used. These rubbery polymers may be used alone or in combination of two or more.
The polymerization method for obtaining the methacrylic resin (B) is not particularly limited, and for example, a conventionally known method such as a bulk polymerization method, a solution polymerization method, a suspension polymerization method, and an emulsion polymerization method may be used. Can be. In particular, in consideration of the transparency of the obtained laminate, it is preferable to employ a polymerization method other than emulsion polymerization.

Specific examples of the solvent used in the solution polymerization method include, but are not particularly limited to, organic solvents such as toluene, xylene, ethylbenzene, methyl isobutyl ketone, and methyl ethyl ketone. As the polymerization initiator used for obtaining the methacrylic resin (B), a well-known one conventionally used for polymerization of methyl methacrylate can be used. Specifically, for example, lauroyl peroxide,
Radical polymerization initiators such as organic peroxides such as t-butyl peroxyisopropyl carbonate; azo compounds such as 2,2-azobisisobutyronitrile;
These polymerization initiators may be used alone or in combination of two or more. The amount of the polymerization initiator to be used may be appropriately set according to the combination of the monomers used, the reaction conditions, and the like, and is not particularly limited.

In the polymerization for obtaining the methacrylic resin (B), a chain transfer agent may be added. As the chain transfer agent, well-known ones conventionally used for polymerization of methyl methacrylate can be used. Among them, a sulfur-based chain transfer agent is particularly preferable.
-Butyl mercaptan, n-dodecyl mercaptan, mercaptan-based chain transfer agents such as thioglycolic acid are excellent in heat stability improving ability, and are easily available.
Particularly preferred. These chain transfer agents may be used alone or in combination of two or more. The amount of the chain transfer agent may be appropriately set according to the combination of the monomers to be used, the reaction conditions, and the like, and is not particularly limited.

The methacrylic resin (B) may contain various additives as necessary. Examples of the additive include, but are not particularly limited to, antioxidants such as hindered phenol, phosphorus, and sulfur; reinforcing materials such as glass fiber; phenyl salicylate, 2 (2′-
Ultraviolet absorbers such as (hydroxy-5-methylphenyl) benzotriazole and 2-hydroxybenzophenone;
Flame retardants such as tris (dibromopropyl) phosphate, ethylene tetrabromide, antimony oxide and zinc borate; antistatic agents such as anionic, cationic, nonionic and amphoteric surfactants; inorganic pigments and organic pigments , A coloring agent such as a dye; and the like. 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 methacrylic resin (B) in the present invention contains, in addition to the methacrylic resin (B), another thermoplastic resin within a range not to impair the effects of the present invention. You can also. However, in this case, it is preferable that the content of the structural unit derived from methyl methacrylate in the total thermoplastic resin obtained by combining the methacrylic resin (B) and another thermoplastic resin is 85% by weight or more. . The layer containing the methacrylic resin (B) in the present invention may be usually formed by molding the methacrylic resin (B) into a film, a sheet or the like. Molding is 10
It is preferably performed at 0 to 350 ° C., more preferably at 15
The temperature is 0 to 300 ° C., but may be appropriately set according to the properties of the resin such as heat resistance, and is not particularly limited. The molding method is not particularly limited, and examples include injection molding, blow molding, and extrusion molding. When the methacrylic resin (B) is used as a sheet, the thickness is preferably 0.5 to 10 mm.
When used in the form of a film, 50 to 500
A thickness of μm is preferred.

The methacrylic resin (B) can be used as a foam sheet if necessary. The density of the foam is preferably 0.05 to 0.3 g / cm ³ . If the density is less than 0.05 g / cm ^3, the rigidity becomes poor, while when it exceeds 0.3 g / cm ^3, the sheet is formed is lowered hard. <Laminate> The laminate of the present invention comprises the thermoplastic resin (A)
And a layer containing the methacrylic resin (B). At this time,
The ratio of the thicknesses of both layers is such that the thickness (A ′) of the layer composed of the thermoplastic resin (A) / the thickness (B ′) of the layer composed of the methacrylic resin (B) = 1/99 to 50/50 is important. By setting the thickness of both layers in the above range, it is possible to achieve both the resistance such as solvent resistance and hot water resistance, and the mechanical strength and impact resistance.

In the present invention, the thermoplastic resin (A)
The method for laminating the layer and the methacrylic resin (B) layer is not particularly limited, and a general method can be employed. For example, at least one of a film or a foam, a method of heating and pressure bonding, a method of applying an adhesive resin in advance on at least one surface, and a method of heating and pressure bonding, and the like. Is preferred because the process is simple. The laminate of the present invention,
The methacrylic resin (B) layer may have a thermoplastic resin (A) layer on one surface or may have a thermoplastic resin (A) layer on both surfaces. In the case of having a thermoplastic resin (2) layer on one side,
A laminate excellent in resistance to a solvent or hot water from one direction is obtained, and a laminate having excellent resistance to a solvent or hot water from both directions is obtained when a thermoplastic resin (2) layer is provided on both sides. Is obtained. That is, the laminate of the present invention exhibits resistance to hot water and solvents by the thermoplastic resin (A) layer, and retains mechanical strength and impact resistance by the methacrylic resin (B) layer. The lamination form may be set as appropriate.

The laminate of the present invention may have a third layer in addition to the thermoplastic resin (A) layer and the methacrylic resin (B) layer depending on desired characteristics. In this case, it is important to dispose a layer made of the thermoplastic resin (A) on at least one surface in order to exert the effect of the present invention against a solvent or hot water. Examples of the third layer include a colored layer using a thermoplastic resin (A), a methacrylic resin (B), or another thermoplastic resin, and a reinforcing layer containing a filler or the like. The laminate of the present invention is preferably in the form of a sheet in that 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.

In the laminate of the present invention, ASTM-D
The total light transmittance measured by a method according to -1003 is 8
It is preferably at least 5%, more preferably at least 88%, most preferably at least 90%. The total light transmittance is
It is a measure of transparency, and if it is less than 85%, the transparency is reduced and it cannot be used for the originally intended use. In the laminate of the present invention, ASTM-D-10
It is preferable that the haze value measured by a method according to 03 is 5% or less, preferably 3% or less, more preferably 1% or less. The haze value is a measure of transparency, and if it exceeds 5%, the transparency is reduced, and it cannot be used for the originally intended use.

In the laminate of the present invention, the notch (no
ASTM-D-2 except that a test piece without tch) was used.
The impact strength (Izod value) measured by a method according to No. 56 is 147 N · cm / cm ² (15 kgf · cm /
cm ² ) or more, more preferably 196 N · cm / cm ² (20 kgf · cm / cm).
² ) Above, most preferably 235 N · cm / cm ²
(24 kgf · cm / cm ² ) or more. The transparent thermoplastic resin laminate of the present invention has resistance to a solvent or hot water,
Because it has both mechanical strength and impact resistance,
For example, a transparent optical lens, an optical element (for example, a light guide, a plastic optical fiber, a light-diffusing planar molded body, etc. which can be used for illumination of various instruments or illumination of various displays and signboards), OA equipment, automobiles and the like It can be applied to various applications such as transparent parts (for example, lenses for laser beam printers, head lenses for vehicles, lamp lenses used for fog lamps, signal lights, etc.). In particular, it can be suitably used for applications such as bathtub surface resin.

[0040]

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”, and the description of “%” indicates “% by weight”. In addition, each analysis in an Example 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 were determined by gas chromatography using the amount of unreacted monomer in the obtained polymerization reaction mixture. (Manufactured by 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 excess 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 Corporation) Measuring conditions: Sample amount 5 to 10 mg Heating rate 10 ° C / min Atmosphere Nitrogen flow 200 ml / min Method Stepwise isothermal control method (60 to 500 ° C) (Weight average molecular weight) The weight average molecular weight of the polymer is 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) The thermal analysis of the resin was performed using DSC (manufactured by Rigaku Corporation, device name: DSC-8230). In addition, the glass transition temperature (Tg) is ASTM-D-341.
According to No. 8, it was determined by the midpoint method.

(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 , the F
T-NMRUNITY + 400 (Varian
Was used for the measurement. (Transparency of Laminate) As an index of the transparency, the total light transmittance of the obtained laminate (thickness: 2.1 mm) was calculated using ASTM D1.
003, turbidity meter (manufactured by Nippon Denshoku Industries Co., Ltd., device name:
NDH-1001DP).

(Impact Resistance of Laminate) According to ASTM-D-256, except that a test piece without notch obtained by cutting out the obtained laminate was used as an index of impact resistance.
The impact strength (Izod value) was measured using an Izod impact tester (manufactured by Toyo Seiki Co., Ltd.). (Hot water resistance of laminate) The laminate was cut into a size of 5 cm x 5 cm, one surface was immersed in hot water at 90 ° C, left standing for 100 hours, and then its appearance was observed. (Solvent Resistance of Laminate) The laminate was cut into 5 cm × 5 cm, and one side was immersed in methanol and left for 7 days, or immersed in xylene and left for 3 days, and the appearance was observed.

REFERENCE EXAMPLE 1 In a 30 L reactor equipped with a stirrer, a temperature sensor, a cooling pipe, and a nitrogen introducing pipe, 10 parts of methyl 2- (hydroxymethyl) acrylate, 40 parts of methyl methacrylate, and 50 parts of toluene 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 0.1 part of a mixture of methyl phosphate / dimethyl phosphate (manufactured by Tokyo Kasei Kogyo Co., Ltd.) based on 100 parts of the polymer solution are added and refluxed under nitrogen (95%). 〜100 ° C.) for 5 hours. A part of the obtained reaction solution was taken out, and dynamic TG was measured. As a result, a weight reduction rate of 0.62% was detected. Next, the obtained polymer solution is subjected to a barrel temperature of 250 ° C., a rotation speed of 100 rpm, and a degree of vacuum of 13.
3 to 400 hPa, a vent type screw twin screw extruder with one rear vent and one fore vent (diameter = 2
9.75 mm, L / D = 30)
The mixture was introduced at a processing rate of Kg / hour, subjected to cyclization condensation reaction and devolatilization in the extruder, and extruded to obtain transparent thermoplastic resin (A-1) pellets.

The color YI of the pellet was 0.8. When the dynamic TG of the obtained pellets was measured, a weight reduction rate of 0.2% was detected.
The weight average molecular weight of the pellet was 165,000.
And the glass transition temperature was 134 ° C. The pellet was analyzed by infrared absorption spectrum analysis and ¹³ C
-NMR spectrum analysis confirmed that the resin had a lactone ring structure in the skeleton. Reference Example 2 In a 200 L SUS autoclave, 96 parts of methyl methacrylate, 4 parts of methyl acrylate, 0.3 part of lauroyl peroxide, 0.36 part of n-dodecyl mercaptan, 1,6-hexanediol diacrylate 0 .113 parts, ion-exchanged water 200 parts, and sodium polymethacrylate 1 part were added and mixed, and heated and heated under a nitrogen atmosphere to initiate polymerization at 80 ° C. After a lapse of 90 minutes, polymerization was carried out at 100 ° C. for 60 minutes. afterwards,
After washing, dehydration and drying, methacrylic resin (B-1)
As a bead-like polymethyl methacrylate (PMM
A) A polymer was obtained. The content (weight ratio) of methyl methacrylate in the obtained polymer was 95.0%. Also,
The weight average molecular weight of this polymer was 150,000.

Example 1 A film having a thickness of 100 μm was formed using the thermoplastic resin (A-1) obtained in Reference Example 1. On the other hand, a sheet having a thickness of 2.0 mm was formed using the methacrylic resin (B-1) obtained in Reference Example 2. Next, the obtained thermoplastic resin (A-1) film and a methacrylic resin (B-1) sheet were bonded at 180 ° C. by a hot roll to form a laminate. The obtained laminate was cut into 5 cm × 5 cm, and a thermoplastic resin (A-
After the surface on which 1) was laminated was left in hot water at 90 ° C. for 100 hours, its appearance was observed, but no discoloration or deformation was found. After the surface on which the thermoplastic resin (A-1) was laminated was left in methanol for 7 days, the appearance was observed, but no discoloration or deformation was found. In addition, similarly, after being left in xylene for 3 days, its appearance was observed, but no discoloration or deformation was found. A test piece was cut out from the obtained laminate and subjected to an impact resistance test. The result was 265 N · cm / cm ² . The total light transmittance of the laminate was 92%.

Comparative Example 1 A sheet having a thickness of 2.1 mm was formed using the methacrylic resin (B-1) obtained in Reference Example 2. The obtained methacrylic resin sheet is 5 cm ×
After cutting to 5 cm and leaving one side in hot water of 90 ° C. for 100 hours, when the appearance was observed, remarkable cloudiness was observed.
Also, the sheet was deformed. Further, one side was left in methanol for 7 days, and the appearance was observed. As a result, the surface was attacked by methanol and the smoothness was lost. When the appearance was observed after similarly standing in xylene for 3 days, the surface was damaged by xylene and the smoothness was lost. A test piece was cut out from the obtained methacrylic resin sheet and subjected to an impact resistance test. The result was 263 N · cm / cm ² . Also,
The total light transmittance of this methacrylic resin sheet was 93%.

Comparative Example 2 Using the thermoplastic resin (A-1) obtained in Reference Example 1, a sheet having a thickness of 2.1 mm was formed. The obtained thermoplastic resin sheet was cut into a size of 5 cm × 5 cm, and one surface was left in hot water at 90 ° C. for 100 hours. The appearance was observed, but no discoloration or deformation was found. After leaving one side in methanol for 7 days, the appearance was observed, but no discoloration or deformation was found. In addition, similarly, after being left in xylene for 3 days, its appearance was observed, but no discoloration or deformation was found.

A test piece was cut out from the obtained thermoplastic resin sheet and subjected to an impact resistance test. As a result, 186 N · cm / cm ²
Met. The total light transmittance of the thermoplastic resin sheet was 92%.

[0052]

According to the present invention, it is possible to provide a transparent thermoplastic resin laminate having excellent resistance to hot water and solvents, and excellent mechanical strength and impact resistance.

 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Minoru Yamaguchi 5-8, Nishiobari-cho, Suita-shi, Osaka Nippon Shokubai Co., Ltd. F-term (reference) 4F100 AK01A AK25B BA02 BA25A BA25B GB32 GB48 JB07 JB16A JK01 JK10 JN01 YY00A YY00B 4J100 AL03P AL08P AL09P AL29Q BA11H BC04P BC43P BC53H CA04 DA36 DA51 DA52 DA62 HA17 JA32

Claims (3)

[Claims] 1. A layer containing a 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, and methyl methacrylate A layer containing a methacrylic resin (B) obtained by polymerizing a monomer component containing 85% by weight or more, and a thickness (A ′) of a layer containing the thermoplastic resin (A) and the methacrylic resin. The ratio of the layer containing (B) to the thickness (B ′) is (A ′) / (B ′) = 1/99.
50/50, a transparent thermoplastic resin laminate. 2. The lactone ring structure of the thermoplastic resin (A) is a structure represented by the following general formula (1):
The transparent thermoplastic resin laminate according to claim 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 contain an oxygen atom. ) 3. The transparent thermoplastic resin laminate according to claim 1, which is in the form of a sheet.