JP2001293836A - Polycarbonate resin laminate - Google Patents

Abstract

(57) Abstract: A laminate is formed by a method such as insert molding, and furthermore, even when a member to be inserted is covered with a protective film, optical distortion is small and moisture resistance and heat resistance are improved. Provided is a polycarbonate resin laminate excellent in long-term properties. SOLUTION: This is a laminate in which a plurality of layers made of polycarbonate resin are substantially in contact with each other.
Layer) is 100% by mole of the total of the phenolic end groups and the non-phenolic end groups, and the amount (x) of the phenolic end groups is 2
The other layer (layer B) is composed of less than 0 mol% of the polycarbonate resin (component A), and the other layer (layer B) has an amount of phenolic terminal group (y ) Comprises 5 to 80 mol% of a polycarbonate resin (component (B)).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a polycarbonate resin laminate. More specifically, the present invention relates to a laminate of a polycarbonate resin having a specific phenolic terminal amount, which is excellent in low distortion such as optical distortion, and also has excellent long-term properties such as wet heat resistance. .

[0002]

2. Description of the Related Art In recent years, products with different functions have been added to each layer of the product in order to increase the value of the product, such as enhancing the functionality and design of the product, and saving resources and environmental measures by recycling and eliminating painting. Design is desired. In particular, there is the highest demand for adding a specific function to the product surface to increase added value.

[0003] In response to such demands, conventionally, printing or hard coating is applied to the surface of a thermoplastic resin sheet, the sheet is inserted into the surface of a mold cavity or the surface of a core, and a thermoplastic resin is placed in the mold cavity. There has been proposed a method in which a sheet and a molded product are integrated by filling by an injection molding method, and value is added to a surface portion. In such a case, in order to strengthen the adhesiveness between the sheet portion and the thermoplastic resin, the thermoplastic resin forming the sheet is made of the same type as the thermoplastic resin injected and filled into the mold forming the molded article body. (Japanese Patent Application Laid-Open Nos. 60-92586 and 60-19551).
No. 5 publication).

A polycarbonate resin laminate having a hard coat is produced by such a production method, and a polycarbonate resin laminate having excellent transparency and strength and excellent surface hardness can be obtained. Is not enough in the field where is required. In particular, when manufacturing a laminate having such good optical properties by the above method, it is necessary to apply a protective film to protect such a sheet molded product until it is inserted into a mold. When it is applied, there is a drawback that the optical distortion of the whole laminate tends to increase.

On the other hand, it is necessary to maintain a sufficient strength of the laminate as a whole for a long period of time, but no such laminate has been sufficiently considered.

[0006]

An object of the present invention is to form a laminate by a method such as insert injection molding.
It is still another object of the present invention to provide a polycarbonate resin laminate having less distortion even when a member to be inserted is covered with a protective film and having excellent long-term properties such as wet heat resistance. As a result of intensive studies to solve the above problems, the present inventors have found that the above problems can be solved by laminating a polycarbonate resin having a specific phenolic terminal amount, and have reached the present invention.

[0007]

According to the present invention, there is provided a laminate comprising a plurality of polycarbonate resin layers substantially in contact with each other, wherein one layer (layer A) has a phenolic terminal group and a non-phenolic terminal group. Consisted of a polycarbonate resin (component A) with less than 20 mol% of phenolic end groups (x) in a total of 100 mol% of groups, and one other layer (B
Layer) contained 100 mol% of phenolic terminal groups and non-phenolic terminal groups, and the amount (y) of phenolic terminal groups was 5%.
The present invention relates to a polycarbonate resin laminate characterized by being composed of up to 80 mol% of a polycarbonate resin (component B).

The polycarbonate resin of the present invention is generally prepared by interfacial polycondensation of a dihydric phenol and a carbonate precursor,
In addition to those obtained by a reaction by a melt transesterification method, those obtained by polymerizing a carbonate prepolymer by a solid-phase transesterification method or those obtained by polymerizing by a ring-opening polymerization method of a cyclic carbonate compound.

Representative examples of the dihydric phenol used herein include hydroquinone, resorcinol, 4,4
4'-dihydroxydiphenyl, bis (4-hydroxyphenyl) methane, bis {(4-hydroxy-3,5-
Dimethyl) phenyl @ methane, 1,1-bis (4-hydroxyphenyl) ethane, 1,1-bis (4-hydroxyphenyl) -1-phenylethane, 2,2-bis (4
-Hydroxyphenyl) propane (commonly known as bisphenol A), 2,2-bis} (4-hydroxy-3-methyl)
Phenyl {propane, 2,2-bis {(4-hydroxy-3,5-dimethyl) phenyl} propane, 2,2-bis {(4-hydroxy-3,5-dibromo) phenyl}
Propane, 2,2-bis {(3-isopropyl-4-hydroxy) phenyl} propane, 2,2-bis} (4-
(Hydroxy-3-phenyl) phenyl} propane, 2,
2-bis (4-hydroxyphenyl) butane, 2,2-
Bis (4-hydroxyphenyl) -3-methylbutane,
2,2-bis (4-hydroxyphenyl) -3,3-dimethylbutane, 2,4-bis (4-hydroxyphenyl) -2-methylbutane, 2,2-bis (4-hydroxyphenyl) pentane, 2, 2-bis (4-hydroxyphenyl) -4-methylpentane, 1,1-bis (4-
(Hydroxyphenyl) cyclohexane, 1,1-bis (4-hydroxyphenyl) -4-isopropylcyclohexane, 1,1-bis (4-hydroxyphenyl)-
3,3,5-trimethylcyclohexane, 9,9-bis (4-hydroxyphenyl) fluorene, 9,9-bis {(4-hydroxy-3-methyl) phenyl} fluorene, α, α′-bis (4- Hydroxyphenyl) -o-
Diisopropylbenzene, α, α′-bis (4-hydroxyphenyl) -m-diisopropylbenzene, α, α
α'-bis (4-hydroxyphenyl) -p-diisopropylbenzene, 1,3-bis (4-hydroxyphenyl) -5,7-dimethyladamantane, 4,4'-dihydroxydiphenylsulfone, 4,4'-dihydroxy Diphenyl sulfoxide, 4,4'-dihydroxydiphenyl sulfide, 4,4'-dihydroxydiphenyl ketone, 4,4'-dihydroxydiphenyl ether, 4,4'-dihydroxydiphenyl ester and the like, and these may be used alone or in combination of two or more. Can be mixed and used.

Among them, bisphenol A, 2,2-bis {(4-hydroxy-3-methyl) phenyl} propane, 2,2-bis (4-hydroxyphenyl) butane,
2,2-bis (4-hydroxyphenyl) -3-methylbutane, 2,2-bis (4-hydroxyphenyl)-
3,3-dimethylbutane, 2,2-bis (4-hydroxyphenyl) -4-methylpentane, 1,1-bis (4
A homopolymer obtained from at least one bisphenol selected from the group consisting of -hydroxyphenyl) -3,3,5-trimethylcyclohexane and α, α'-bis (4-hydroxyphenyl) -m-diisopropylbenzene, or Copolymers are preferred. In particular, bisphenol A homopolymer and 1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane and bisphenol A, 2,2-bis {(4-hydroxy- Copolymers with 3-methyl) phenyl} propane or α, α′-bis (4-hydroxyphenyl) -m-diisopropylbenzene are preferably used.

As the carbonate precursor, carbonyl halide, carbonate ester or haloformate is used, and specific examples include phosgene, diphenyl carbonate, dihaloformate of dihydric phenol and the like.

In producing the polycarbonate resin by reacting the above-mentioned dihydric phenol with the carbonate precursor by the interfacial polycondensation method or the melt transesterification method, if necessary, a catalyst, a terminal stopper and an oxidation of the dihydric phenol are required. An inhibitor or the like may be used. Further, the polycarbonate resin may be a branched polycarbonate resin obtained by copolymerizing a trifunctional or higher polyfunctional aromatic compound, or a polyester carbonate resin obtained by copolymerizing an aromatic or aliphatic bifunctional carboxylic acid, Further, a mixture of two or more of the obtained polycarbonate resins may be used.

[0013] Examples of the trifunctional or higher polyfunctional aromatic compound include phloroglucin, phloroglucid, and 4,6-
Dimethyl-2,4,6-tris (4-hydroxydiphenyl) heptene-2,2,4,6-trimethyl-2,4
6-tris (4-hydroxyphenyl) heptane, 1,
3,5-tris (4-hydroxyphenyl) benzene,
1,1,1-tris (4-hydroxyphenyl) ethane, 1,1,1-tris (3,5-dimethyl-4-hydroxyphenyl) ethane, 2,6-bis (2-hydroxy-5-methylbenzyl) ) -4-Methylphenol, 4
-{4- [1,1-bis (4-hydroxyphenyl) ethyl] benzene} -α, α-dimethylbenzylphenol and other trisphenols, tetra (4-hydroxyphenyl) methane, bis (2,4-dihydroxyphenyl) )
Examples thereof include ketone, 1,4-bis (4,4-dihydroxytriphenylmethyl) benzene, trimellitic acid, pyromellitic acid, benzophenonetetracarboxylic acid, and acid chlorides thereof, among which 1,1,1-tris (4-hydroxyphenyl) ethane, 1,1,1-
Tris (3,5-dimethyl-4-hydroxyphenyl)
Ethane is preferred, and 1,1,1-tris (4-hydroxyphenyl) ethane is particularly preferred.

When a polyfunctional compound producing such a branched polycarbonate resin is contained, the proportion is preferably 0.001 to 1 mol%, preferably 0.005 to 0.5 mol%, particularly preferably 0.005 to 1 mol%, based on the total amount of the aromatic polycarbonate. 0.01
~ 0.3 mol%. In particular, in the case of the melt transesterification method, a branched structure may occur as a side reaction, and the amount of such a branched structure is also 3;
It is preferably from 0.5 to 0.5 mol%, particularly preferably from 0.01 to 0.3 mol%. The ratio is ¹
It can be calculated by 1 H-NMR measurement.

The reaction by the interfacial polycondensation method is usually a reaction between dihydric phenol and phosgene, and is carried out in the presence of an acid binder and an organic solvent. As the acid binder, for example, an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide or an amine compound such as pyridine is used.
As the organic solvent, for example, halogenated hydrocarbons such as methylene chloride and chlorobenzene are used. Further, for promoting the reaction, for example, a catalyst such as a tertiary amine such as triethylamine, tetra-n-butylammonium bromide, or tetra-n-butylphosphonium bromide, a quaternary ammonium compound, or a quaternary phosphonium compound may be used. it can. At that time, the reaction temperature is usually 0 to 40 ° C., the reaction time is preferably about 10 minutes to 5 hours, and the pH during the reaction is preferably maintained at 9 or more.

In such a polymerization reaction, a terminal stopper is usually used. Monofunctional phenols can be used as such a terminal stopper. Monofunctional phenols are commonly used as molecular terminators for molecular weight control, such monofunctional phenols are generally phenols or lower alkyl substituted phenols,
Monofunctional phenols represented by the following general formula (1) can be shown.

[0017]

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(Wherein A is a hydrogen atom or a carbon number of 1 to 9)
Is a linear or branched alkyl group or a phenyl group-substituted alkyl group, and r is an integer of 1 to 5, preferably 1 to 3. )

Specific examples of the above monofunctional phenols include phenol, p-tert-butylphenol, p-cumylphenol and isooctylphenol.

Further, other monofunctional phenols include:
Phenols or benzoic acid chlorides having a long-chain alkyl group or aliphatic polyester group as a substituent, or long-chain alkylcarboxylic acid chlorides can also be used. Among these, phenols having a long-chain alkyl group represented by the following general formulas (2) and (3) as a substituent are preferably used.

[0021]

Embedded image

[0022]

Embedded image

(Wherein X is -RO-, -R-CO-O
— Or —RO—CO—, wherein R represents a single bond or a divalent aliphatic hydrocarbon group having 1 to 10, preferably 1 to 5 carbon atoms, and n represents an integer of 10 to 50. Show. )

The substituted phenols of the general formula (2) are preferably those having n of 10 to 30, especially 10 to 26, and specific examples thereof include, for example, decylphenol, dodecylphenol, tetradecylphenol, hexadecylphenol, Octadecylphenol, eicosylphenol, docosylphenol, triacontylphenol and the like can be mentioned.

As the substituted phenols of the general formula (3), compounds wherein X is -R-CO-O- and R is a single bond are suitable, and n is 10-30, especially 10-26.
Are preferred, and specific examples thereof include, for example, decyl hydroxybenzoate, dodecyl hydroxybenzoate,
Examples include tetradecyl hydroxybenzoate, hexadecyl hydroxybenzoate, eicosyl hydroxybenzoate, docosyl hydroxybenzoate and triacontyl hydroxybenzoate. Further, the terminal stoppers may be used alone or in combination of two or more.

The reaction by the melt transesterification method is usually a transesterification reaction between a dihydric phenol and a carbonate ester, and is produced by mixing the dihydric phenol and the carbonate ester while heating in the presence of an inert gas. It is carried out by a method of distilling alcohol or phenol. The reaction temperature varies depending on the boiling point of the produced alcohol or phenol, but is usually in the range of 120 to 350 ° C. In the late stage of the reaction, the system was adjusted to 1.33 × 10 ³ -1.
The alcohol or phenol produced by reducing the pressure to about 3.3 Pa is easily distilled. Reaction time is usually 1-4
About an hour.

Examples of the carbonate ester include an optionally substituted ester such as an aryl group having 6 to 10 carbon atoms, an aralkyl group or an alkyl group having 1 to 4 carbon atoms. Specifically, diphenyl carbonate, bis (chlorophenyl) carbonate, dinaphthyl carbonate, bis (diphenyl) carbonate, dimethyl carbonate, diethyl carbonate, dibutyl carbonate and the like can be mentioned, with diphenyl carbonate being preferred.

A polymerization catalyst can be used to increase the polymerization rate. Examples of such a polymerization catalyst include sodium hydroxide, potassium hydroxide, alkali metal compounds such as sodium and potassium salts of dihydric phenol, and water. Alkaline earth metal compounds such as calcium oxide, barium hydroxide and magnesium hydroxide; nitrogen-containing basic compounds such as tetramethylammonium hydroxide, tetraethylammonium hydroxide, trimethylamine and triethylamine; alkoxides of alkali metals and alkaline earth metals Manganese, organic acid salts of alkali metals and alkaline earth metals, zinc compounds, boron compounds, aluminum compounds, silicon compounds, germanium compounds, organic tin compounds, lead compounds, osmium compounds, antimony compounds Compounds, titanium compounds, usually the esterification reaction, such as zirconium compounds, there can be used a catalyst used in the transesterification reaction. The catalyst may be used alone or in combination of two or more. The amount of the polymerization catalyst used is preferably 1 × 10 ⁻⁸ to 1 ×, based on 1 mol of the dihydric phenol used as the raw material.
It is selected in the range of 10 ⁻³ equivalents, more preferably 1 × 10 ^{−7 to} 5 × 10 ⁻⁴ equivalents.

In such a polymerization reaction, to reduce the number of phenolic terminal groups, for example, bis (chlorophenyl) carbonate, bis (bromophenyl) carbonate, bis (nitrophenyl) carbonate is used later or after completion of the polycondensation reaction. , Bis (phenylphenyl)
Carbonate, chlorophenylphenyl carbonate,
Compounds such as bromophenylphenyl carbonate, nitrophenylphenyl carbonate, phenylphenyl carbonate, methoxycarbonylphenylphenyl carbonate and ethoxycarbonylphenylphenyl carbonate can be added. Among them, 2-chlorophenylphenyl carbonate, 2-methoxycarbonylphenylphenyl carbonate and 2-ethoxycarbonylphenylphenyl carbonate are preferred,
Particularly, 2-methoxycarbonylphenylphenyl carbonate is preferably used.

Further, it is preferable to use a deactivator for neutralizing the activity of the catalyst in such a polymerization reaction. Specific examples of the deactivator include, for example, benzenesulfonic acid, p-toluenesulfonic acid, methylbenzenebenzenesulfonate, ethylbenzenebenzenesulfonate, butylbenzenesulfonate, octylbenzenesulfonate, phenylbenzenesulfonate, and p-toluenesulfone. Sulfonates such as methyl acrylate, ethyl p-toluenesulfonate, butyl p-toluenesulfonate, octyl p-toluenesulfonate, and phenyl p-toluenesulfonate; further, trifluoromethanesulfonic acid, naphthalenesulfonic acid, and sulfonated polystyrene , Methyl acrylate-sulfonated styrene copolymer, 2-phenyl-2-propyl dodecylbenzenesulfonic acid, dodecylbenzenesulfonic acid-2-
Phenyl-2-butyl, tetrabutylphosphonium octylsulfonate, tetrabutylphosphonium decylsulfonate, tetrabutylphosphonium benzenesulfonate, tetraethylphosphonium dodecylbenzenesulfonate, tetrabutylphosphonium dodecylbenzenesulfonate, dodecylbenzenesulfonate Acid tetrahexyl phosphonium salt, dodecyl benzene sulfonic acid tetraoctyl phosphonium salt, decyl ammonium butyl sulfate, decyl ammonium decyl sulfate, dodecyl ammonium methyl sulfate, dodecyl ammonium ethyl sulfate, dodecyl methyl ammonium methyl sulfate, dodecyl dimethyl ammonium tetradecyl sulfate, tetradecyl Dimethyl ammonium Chill sulfate, tetramethylammonium hexyl sulfate, decyltrimethylammonium hexadecyl sulfate, tetrabutylammonium dodecylbenzyl sulfate, tetraethylammonium dodecylbenzyl sulfate, there may be mentioned compounds such as tetramethylammonium dodecylbenzyl sulfate, and the like. Two or more of these compounds can be used in combination.

Among the deactivators, those of the phosphonium salt or ammonium salt type are preferred. The amount of such a catalyst is preferably 0.5 to 50 mol based on 1 mol of the remaining catalyst, and 0.01 to 500 ppm, more preferably 0 to 500 ppm, based on the polycarbonate resin after polymerization. 0.01 to 300 ppm, particularly preferably 0.01 to 100 ppm.

Although the molecular weight of the polycarbonate resin is not specified, if the molecular weight is less than 10,000, the strength becomes insufficient, and if it exceeds 40,000, the moldability deteriorates and it becomes difficult to reduce the strain. Those having a molecular weight of 10,000 to 40,000 are preferable, and
Those having a size of 000 to 30,000 are particularly preferred. Also, two or more polycarbonate resins may be mixed. The viscosity average molecular weight referred to in the present invention is 100 methylene chloride.
The specific viscosity (η _SP ) obtained from a solution in which 0.7 g of a polycarbonate resin is dissolved in 20 ml at 20 ° C. is inserted into the following equation. η _SP /c=[η]+0.45×[η] ² c (where [η]
Is the intrinsic viscosity) [η] = 1.23 × 10 ⁻⁴ M ^0.83 c = 0.7

As the polycarbonate resin of the component A and the component B of the present invention, any of the above-mentioned interfacial polycondensation method and melt transesterification method can be used, but the polycarbonate resin of the component A having a small number of phenolic terminal groups can be used. Is preferably produced by an interfacial polycondensation method, while the polycarbonate resin of component B having a large number of phenolic terminal groups is preferably produced by a melt transesterification method.

In the polycarbonate resin of the component A used in the present invention, the amount of the phenolic terminal group is less than 20% by mole, preferably 100% by mole of the total of the phenolic terminal group and the non-phenolic terminal group of the polycarbonate resin. Is less than 10 mol%. When the amount of the component A is 20 mol% or more, the long-term properties such as the moisture and heat resistance of the laminate are reduced.

On the other hand, the polycarbonate resin of the component B is used in an amount of 5 to 80 mol%, preferably 10 to 65 mol%, of the phenolic terminal group based on 100 mol% of the total of the phenolic terminal group and the non-phenolic terminal group of the polycarbonate resin. , More preferably 20 to 60 mol%. 5 mol%
When the amount is less than the above, it is difficult to suppress optical distortion generated at the interface during the production of the laminate, and when the amount exceeds 80 mol%, the long-term properties such as the heat and humidity resistance of the laminate are deteriorated.

In the present invention, the term "phenolic terminal group" refers to a terminal structure having a phenolic hydroxyl group at the molecular chain terminal, and usually has a structure in which a dihydric phenol component constitutes the molecular chain terminal. . On the other hand, a non-phenolic terminal group is a terminal structure that does not contain a phenolic hydroxyl group at the molecular chain terminal, and is usually a structure in which a terminal terminator forms a molecular chain terminal, or a method of melt transesterification. In this case, the structure is such that the carbonate ester constitutes the terminal of the molecular chain.

The amounts of the phenolic terminal group and the non-phenolic terminal group in the present invention refer to the values obtained from the intensity area ratios of the corresponding peaks using ¹ H-NMR.

In the present invention, various production methods can be employed for producing a laminate.
This is suitable for a production method in which the components are substantially laminated on the surface of the component B with shearing. Preferably, such a production method includes an insert injection molding method and a multicolor injection molding method. That is, this is a method in which a molded article formed from the B component is placed in a mold as a B layer, and the A component is filled into the mold by injection molding and laminated as an A layer. In the case of the insert injection molding method, the molded article composed of the B component is manufactured in advance in a separate step, while in the case of the multicolor injection molding method, the molded article composed of the B component is produced in the same molding machine. It will be manufactured in the previous process.

Particularly preferred as the production method of the present invention is a method in which a printed layer or a hard coat layer, particularly a hard coat layer, is provided on the outermost surface of the layer B which is a molded article formed from the component B. It is a thing. From such a relationship, the most preferable manufacturing method is a method of forming the A layer by insert injection molding of the A component into a mold in which a molded body for forming the B layer is inserted.

Further, according to the present invention, the surface of the molded body composed of the inserted component B, which is in contact with the layer A, is covered with a protective film. After removing the protective film, a laminate with the layer A is formed. In particular, this effect is exhibited when it is used.

It is considered that there are various factors that cause distortion such as optical distortion at the interface portion when molding such a laminate, and non-uniform flow at the interface portion is a main factor. It is thought that it becomes. The reason why the optical distortion is reduced when the polycarbonate resin of the B layer has a specific phenolic terminal amount is unknown, but it is considered that the suppression of such non-uniformity of the flow is involved. In particular, when protected by a masking material, it is considered that a small amount of the remaining sticky substance and its unevenness tend to cause uneven flow of the interface.

As the protective film in the present invention, a base material such as polyethylene, polypropylene, polyethylene terephthalate, etc. may be coated on an ethylene vinyl acetate copolymer, a polyethylene oligomer, an alkyl (meth) acrylate polymer, an alkyl (meth) acrylate copolymer, a polyorganosiloxane, And those having an adhesive layer such as a copolymer composed of these monomer components. Among them, polyethylene having a thickness of 20 to 100 μm, a substrate having an adhesive layer such as a 10 to 30 μm ethylene vinyl acetate copolymer or a polyethylene oligomer on a substrate such as polypropylene is preferably used, and particularly a polyethylene substrate having an ethylene vinyl acetate copolymer. Those having an adhesive layer are preferably used. The adhesive strength between the polycarbonate resin molded body and the protective film is 0.1%.
幅 1 N / 50 mm width is preferred. A protective film having an adhesive force in such a range has a sufficient adhesive force and thus functions as a protective film, and is less likely to cause adhesive residue when peeled off. Here, the adhesive force means that the protective film adhered to the polycarbonate resin sheet with a width of 50 mm has an edge of the protective film perpendicular to the polycarbonate resin sheet at a temperature of 20 ° C. (at a peeling angle of 90 °) and a peeling speed of 200 mm. / Min is a value obtained by measuring the adhesive strength when peeled at a speed of / min.

In the present invention, it is not necessary for the polycarbonate resins to be in contact with each other on all surfaces where the layer A and the layer B are in contact with each other. A print layer, a void, or the like may exist on a part of one surface.

In the present invention, particularly preferred examples of the molded article for forming the layer B include a plate-like article such as a sheet and a molded article obtained by subjecting such a sheet to secondary processing by vacuum molding or thermoforming. Such a sheet can be produced by a general method such as a melt extrusion method, an inflation method, a continuous casting method, a cell casting method, a solution casting method or a powder molding method. Further, in these production methods, a method of directly performing melt extrusion from a molten state such as a melt transesterification reaction in a production process of a raw material resin, or directly performing the above solution casting from a solution state after polymerization, to obtain a thermal history. It is also possible to obtain a sheet with a small number.

Further, in the present invention, it is preferable to use a sheet in which the surface opposite to the interface between the layer A and the layer B in the sheet has been subjected to a treatment such as hard coating or printing in advance.

In the present invention, the hard coat agent includes
Examples include a silicone resin-based hard coat agent and an organic resin-based hard coat agent. The silicone resin-based hard coat agent is a resin having a siloxane bond, for example, a mixture of trialkoxysilane and tetraalkoxysilane or a partial hydrolyzate of an alkylated product thereof, and a mixture of methyltrialkoxysilane and phenyltrialkoxysilane. Decomposed products, partially hydrolyzed condensates of colloidal silica-filled organotrialkoxysilanes and the like can be mentioned. These include alcohols and the like generated during the condensation reaction, and further, if necessary, any organic solvent,
The organic solvent may be dissolved or dispersed in water or a mixture thereof, and examples of the organic solvent include lower fatty alcohols, polyhydric alcohols and ethers and esters thereof. Note that various surfactants, for example, siloxane-based or alkyl fluoride-based surfactants, may be added to the hard coat layer in order to obtain a smooth surface state. Examples of the organic resin-based hard coat agent include a melamine resin, a urethane resin, an alkyd resin, an acrylic resin, and a polyfunctional acrylic resin. Here, examples of the polyfunctional acrylic resin include resins such as polyol acrylate, polyester acrylate, urethane acrylate, epoxy acrylate, and phosphazene acrylate. Among these hard coat agents, silicone resin hard coat agents which are excellent in long-term weather resistance and have relatively high surface hardness are preferable. In particular, after forming a primer layer composed of various resins, a silicone resin hard coat agent is formed thereon. It is preferable to form a cured layer adjusted from a coating agent.

Examples of the resin forming the primer layer include urethane resins, acrylic resins, polyester resins, epoxy resins, melamine resins, amino resins, and polyester acrylates, urethane acrylates, epoxy acrylates comprising various blocked isocyanate components and polyol components. Examples include various polyfunctional acrylic resins such as phosphazene acrylate, melamine acrylate, and amino acrylate, and these can be used alone or in combination of two or more. Of these, acrylic resin and polyfunctional acrylic resin are particularly preferably 50% by weight for polycarbonate resin,
More preferably, those containing 60% by weight or more can be mentioned, and those made of acrylic resin are particularly preferable.

Further, the resin forming the primer layer of the silicone resin-based hard coat agent of the present invention includes a light stabilizer and an ultraviolet absorber described later, a catalyst for the silicone resin hard coat agent, a heat / photopolymerization initiator, Inhibitors, silicone defoamers,
It may contain leveling agents, thickeners, sedimentation inhibitors, anti-sagging agents, flame retardants, various additives for organic / inorganic pigments / dyes, and auxiliary additives.

As the curing method, known methods such as ultraviolet curing, heat curing, electron beam curing, infrared irradiation and hot air drying may be used alone or in combination. In such a case, particularly when the stretching ratio of the resin sheet locally increases as described above, after the hard coat agent is cured to the extent that it is not completely cured, without shaping, or without shaping Then, after molding to obtain a multilayer structure molded article, a method of completely curing the hard coat agent can be adopted. In addition, a hard coat agent is applied as a sol or gel having a partially cross-linked structure, and thereafter, without shaping, or after shaping and shaping to form a multilayer structure molded article, the hard coat agent is applied. A method of completely curing can be adopted.

Known methods such as a bar coating method, a spray coating method, and a roll coating method can be used as a method of applying the hard coat film forming raw material. The thickness of the lamination sheet thus obtained is determined by the appearance of a molded product, impact resistance, abrasion resistance, weather resistance and the like. The thickness is preferably 1 to 50 μm, more preferably 3 to 30 μm
It is. If the thickness of the hard coat film is less than 1 μm, sufficient abrasion resistance cannot be obtained, and if the thickness is more than 50 μm, the flexibility of the coating film decreases and cracks occur due to bending and the like. At the time of coating, an organic solvent may be added as a diluent to the raw material for forming a hard coat film. Organic solvents that can be used include butyl acetate, ethyl acetate, toluene, isopropanol and the like. Its usage is
The range of 10 to 100 parts is preferable for 100 parts of solids.

In the present invention, characters and patterns can be formed on a part of the resin sheet by printing and used.

As a printing method, a conventionally known printing method such as gravure printing, lithographic printing, flexographic printing, dry offset printing, pad printing, screen printing and the like can be used according to the product shape and printing use.

The composition of the printing ink used in printing can be a resin or an oil as a main component. Examples of the resin include natural resins such as rosin, Gilsonite, shellac and copearl, and phenol. System and its derivatives, amino resin, butylated urea, melamine resin, polyester alkyd resin, styrene resin, acrylic resin, phenol resin, epoxy resin, polyamide resin, polycarbonate resin, saturated polyester resin, amorphous polyarylate resin, Amorphous polyolefin resin, vinyl chloride resin, vinyl acetate resin, vinyl chloride
Synthetic resins such as vinyl acetate copolymer, butyral resin, methylcellulose resin, ethylcellulose resin, and urethane resin can be used. In particular, when printing is performed on the interface side surface between the layer A and the layer B in the layer B, an ink component having high heat resistance is required. In such a case, a resin such as a polycarbonate resin or an amorphous polyarylate resin is used. Are preferred. In addition, a desired color can be adjusted by using a pigment or a dye in the printing ink.

On the other hand, as other surface treatments, it is also possible to apply a fluorine-based water / oil repellent coat or a water immersion coat with a photocatalyst or the like.

The thickness of the resin sheet is usually 5
0 to 2000 μm, preferably 100 to 1000 μm,
More preferably, it is 200 to 700 μm.

The surface of the molded article forming the layer B of the present invention which is in contact with the layer A may be subjected to printing or the like, and similarly, the surface of the layer B which is in contact with the layer A. May be not only a simple plane but also a three-dimensional pattern on the surface. By providing such a three-dimensional pattern and having light transmissivity, it is possible to obtain a polycarbonate laminate having a high degree of design and optical functions.

Here, the three-dimensional pattern refers to three-dimensional irregularities in which optical changes and non-uniformities can be visually recognized from the surface. Such a shape may be any of characters, figures, symbols, and a combination thereof. You may. Further, such a shape includes not only design properties but also optically usable regular figures such as a lenticular lens and a set of dots that can be a diffusion starting point. In addition, such three-dimensional irregularities do not necessarily need to be visible to the naked eye, and due to the prism effect of the irregularities, optical effects that cannot be obtained on a normal plane (such as iridescent light). What is necessary is just to have.

The polycarbonate resin of the component A and the component B of the present invention may contain a release agent. As the release agent, a saturated fatty acid ester is generally used, for example, monoglycerides such as stearic acid monoglyceride, polyglycerin fatty acid esters such as decaglycerin decastearate and decaglycerin tetrastearate, and lower fatty acids such as stearic acid stearate. Esters, higher fatty acid esters such as sebacic acid behenate, erythritol esters such as pentaerythritol tetrastearate, and other phenyl group-containing silicon compounds are also used. The release agent is used in an amount of 0.01 to 1 part by weight per 100 parts by weight of the polycarbonate resin.

Further, a phosphorus-based heat stabilizer can be added to the polycarbonate resin of the present invention, if necessary. As the phosphorus-based stabilizer, any of phosphite-based, phosphonite-based, and phosphate-based stabilizers can be used.

Various phosphite-based stabilizers in the present invention can be used. Specifically, for example, general formula (4)

[0061]

Embedded image

[Wherein R ¹ is hydrogen or C 1-20
An alkyl group, an aryl group or alkaryl group having 6 to 20 carbon atoms, an aralkyl group having 7 to 30 carbon atoms, or a halo or alkylthio (the alkyl group has 1 to 3 carbon atoms)
0) or a hydroxy substituent, and the three R ^{1 s} can be either the same as each other or different from each other, and the cyclic structure can also be selected by being derived from a dihydric phenol. ] It is a phosphite compound represented by these.

In a more preferred embodiment of the general formula (4), the following general formula (5)

[0064]

Embedded image

[0065] [wherein R ² and R ³ is hydrogen or an alkyl group having 1 to 20 carbon atoms, an aryl group or alkyl aryl group having 6 to 20 carbon atoms, an aralkyl group having 7 to 30 carbon atoms, R ² And R ³ are not hydrogen at the same time, and they can be either the same or different. And a phosphite compound represented by the following formula:

The general formula (6)

[0067]

Embedded image

[In the formula, R ⁴ and R ⁵ are each hydrogen and have 1 carbon atom.
An alkyl group having 20 to 20 carbon atoms, an aryl group or an alkylaryl group having 6 to 20 carbon atoms, an aralkyl group having 7 to 30 carbon atoms, a cycloalkyl group having 4 to 20 carbon atoms,
Represents 25 2- (4-oxyphenyl) propyl-substituted aryl groups, which can be selected when they are the same or different from each other. The cycloalkyl group and the aryl group can be selected from those not substituted with an alkyl group and those substituted with an alkyl group. And a phosphite compound represented by the following formula:

The general formula (7)

[0070]

Embedded image

[Wherein R ⁶ and R ⁷ are alkyl groups having 12 to 15 carbon atoms. Note that R ⁶ and R ⁷ can be either the same or different. And a phosphite compound represented by the following formula:

Examples of the phosphonite stabilizer include a phosphonite compound represented by the following general formula (8) and a phosphonite compound represented by the following general formula (9).

[0073]

Embedded image

[Wherein, Ar ¹ represents an aryl group or an alkylaryl group having 6 to 20 carbon atoms, or 15 to 2 carbon atoms.
5 represents a 2- (4-oxyphenyl) propyl-substituted aryl group, and four Ar ^{1 s} may be the same as or different from each other. ]

[0075]

Embedded image

[Wherein, Ar ² represents an aryl group or an alkylaryl group having 6 to 20 carbon atoms, or an aryl or alkylaryl group having 15 to 2 carbon atoms.
5 represents a 2- (4-oxyphenyl) propyl-substituted aryl group, and two Ar ^{2 s} may be the same as or different from each other. ]

In the present invention, among the above-mentioned phosphite compounds and phosphonite compounds, more preferred phosphorus-based stabilizers include the phosphite compound represented by the above formula (5) (component E1) and the above-mentioned formula (8) )
(E2 component) and the phosphonite compounds represented by the above-mentioned general formula (9) (E3 component) can be mentioned, and these can be used alone or in combination of two or more, and more preferably the above-mentioned general formula (5) At least 5% by weight of 100% by weight of the E component
This is the case.

Preferred specific examples of the phosphite compound corresponding to the general formula (4) include diphenylisooctyl phosphite, 2,2′-methylenebis (4,6-di-tert-butylphenyl) octyl phosphite, Examples include diphenyl mono (tridecyl) phosphite, phenyl diisodecyl phosphite, and phenyl di (tridecyl) phosphite. More preferred specific examples corresponding to the above general formula (5) include triphenyl phosphite, tris (dimethylphenyl) phosphite, tris (diethylphenyl) phosphite, tris (di-iso-propylphenyl) phosphite, Tris (di-n-butylphenyl) phosphite, tris (2,4-di-tert-butylphenyl) phosphite, tris (2,6-di-tert-butylphenyl) phosphite and the like. Dialkyl-substituted phenyl) phosphite is preferred, tris (di-tert-butylphenyl) phosphite is more preferred, and tris (2,4-di-tert-butylphenyl) phosphite is particularly preferred. The above phosphite compounds can be used alone or in combination of two or more.

Preferred specific examples of the phosphite compound corresponding to the above general formula (6) include distearylpentaerythritol diphosphite, bis (2,4-
Di-tert-butylphenyl) pentaerythritol diphosphite, bis (2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite, phenylbisphenol A pentaerythritol diphosphite, dicyclohexylpentaerythritol diphosphite And distearyl pentaerythritol diphosphite, bis (2,4-di-tert-butylphenyl) pentaerythritol diphosphite, bis (2,6-di-ter
(tert-butyl-4-methylphenyl) pentaerythritol diphosphite. Such phosphite compounds can be used alone or in combination of two or more.

Preferred specific examples of the phosphite compound corresponding to the general formula (7) include 4,4'-isopropylidenediphenol ditridecyl phosphite.

Preferred specific examples of the phosphonite compound corresponding to the above general formula (8) include tetrakis (2,4-di-iso-propylphenyl) -4,4 ′
-Biphenylenediphosphonite, tetrakis (2,4-
Di-n-butylphenyl) -4,4'-biphenylenediphosphonite, tetrakis (2,4-di-tert-butylphenyl) -4,4'-biphenylenediphosphonite, tetrakis (2,4-di- tert-butylphenyl) -4,3′-biphenylenediphosphonite, tetrakis (2,4-di-tert-butylphenyl) -3,
3'-biphenylenediphosphonite, tetrakis (2,
6-di-iso-propylphenyl) -4,4'-biphenylenediphosphonite, tetrakis (2,6-di-n
-Butylphenyl) -4,4'-biphenylenediphosphonite, tetrakis (2,6-di-tert-butylphenyl) -4,4'-biphenylenediphosphonite, tetrakis (2,6-di-tert-butyl) Phenyl)-
4,3′-biphenylenediphosphonite, tetrakis (2,6-di-tert-butylphenyl) -3,3 ′
-Biphenylenediphosphonite; tetrakis (di-tert-butylphenyl) -biphenylenediphosphonite is preferred; tetrakis (2,4-di-t
(tert-butylphenyl) -biphenylenediphosphonite is more preferred. This tetrakis (2,4-di-te
(rt-butylphenyl) -biphenylenediphosphonite is preferably a mixture of two or more, specifically, tetrakis (2,4-di-tert-butylphenyl) -4,
4'-biphenylenediphosphonite (E2-1 component),
Tetrakis (2,4-di-tert-butylphenyl)
One kind of -4,3'-biphenylenediphosphonite (E2-2 component) and tetrakis (2,4-di-tert-butylphenyl) -3,3'-biphenylenediphosphonite (E2-3 component) Alternatively, two or more of them can be used in combination, but a mixture of these three is preferred. In the case of three kinds of mixtures, the mixing ratio is E2-1.
Component, E2-2 component and E2-3 component in a weight ratio of 10
The range of 0:37 to 64: 4 to 14 is preferable, and 100:
The range of 40-60: 5-11 is more preferable.

Preferred specific examples of the phosphonite compound corresponding to the above general formula (9) include bis (2,4-di-
iso-propylphenyl) -4-phenyl-phenylphosphonite, bis (2,4-di-n-butylphenyl) -3-phenyl-phenylphosphonite, bis (2,4-di-tert-butylphenyl)- 4-phenyl-phenylphosphonite, bis (2,4-di-te
rt-butylphenyl) -3-phenyl-phenylphosphonite bis (2,6-di-iso-propylphenyl) -4-phenyl-phenylphosphonite, bis (2,6-di-n-butylphenyl) -3 -Phenyl-
Phenylphosphonite, bis (2,6-di-tert-
Butylphenyl) -4-phenyl-phenylphosphonite, bis (2,6-di-tert-butylphenyl)-
3-phenyl-phenylphosphonite and the like, and bis (di-tert-butylphenyl) -phenyl-phenylphosphonite is preferable, and bis (2,4-di-te
(rt-butylphenyl) -phenyl-phenylphosphonite is more preferred. This screw (2,4-di-tert)
-Butylphenyl) -phenyl-phenylphosphonite is preferably a mixture of two or more, specifically, bis (2,4-di-tert-butylphenyl) -4-phenyl-phenylphosphonite (E3-1 component). )and,
Bis (2,4-di-tert-butylphenyl) -3-
1 of phenyl-phenylphosphonite (E3-2 component)
Species or a combination of two species can be used, but a mixture of the two species is preferred. In the case of two kinds of mixtures, the mixing ratio is preferably in the range of 5: 1 to 4 by weight, more preferably in the range of 5: 2 to 3.

On the other hand, examples of the phosphate stabilizers include tributyl phosphate, trimethyl phosphate, tricresyl phosphate, triphenyl phosphate, trichlorophenyl phosphate, triethyl phosphate, diphenylcresyl phosphate, diphenylmonoorthoxenyl phosphate, tribubutoxyethyl phosphate, and the like. Examples thereof include dibutyl phosphate, dioctyl phosphate, and diisopropyl phosphate, and preferred is trimethyl phosphate.

The composition ratio of the phosphorus stabilizer is as follows:
0.0005 to 1 part by weight, preferably 0.001 to 0.5 part by weight, per 100 parts by weight of the component A.

An antioxidant represented by a hindered phenol compound can also be used for improving weather resistance. Such antioxidants include, for example, vitamin E,
n-octadecyl-β- (4′-hydroxy-3 ′,
5'-di-tert-butylfell) propionate,
2-tert-butyl-6- (3'-tert-butyl-5'-methyl-2'-hydroxybenzyl) -4-methylphenyl acrylate, 2,6-di-tert-butyl-4- (N, N -Dimethylaminomethyl) phenol, 3,5-di-tert-butyl-4-hydroxybenzylphosphonate diethyl ester, 2,2′-methylenebis (4-methyl-6-tert-butylphenol), 2,2′-methylenebis ( 4-ethyl-6-te
rt-butylphenol), 4,4'-methylenebis (2,6-di-tert-butylphenol), 2,
2′-methylenebis (4-methyl-6-cyclohexylphenol), 2,2′-dimethylene-bis (6-α-
Methyl-benzyl-p-cresol) 2,2′-ethylidene-bis (4,6-di-tert-butylphenol), 2,2′-butylidene-bis (4-methyl-6-
tert-butylphenol), 4,4'-butylidenebis (3-methyl-6-tert-butylphenol), triethylene glycol-N-bis-3- (3-
tert-butyl-4-hydroxy-5-methylphenyl) propionate, 1,6-hexanediol bis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, bis [2-tert- Butyl-4-methyl 6- (3-tert-butyl-5-methyl-2-hydroxybenzyl) phenyl] terephthalate, 3,9-bis {2- [3- (3-tert-butyl-4-hydroxy-5) -Methylphenyl) propionyloxy] -1,1, -dimethylethyl} -2,4.
8,10-tetraoxaspiro [5,5] undecane,
4,4-thiobis (6-tert-butyl-m-cresol), 4,4′-thiobis (3-methyl-6-ter
t-butylphenol), 2,2′-thiobis (4-methyl-6-tert-butylphenol), bis (3
5-di-tert-butyl-4-hydroxybenzyl)
Sulfide, 4,4'-di-thiobis (2,6-di-t
tert-butylphenol), 4,4′-tri-thiobis (2,6-di-tert-butylphenol), 2,
4-bis (n-octylthio) -6- (4-hydroxy-3 ′, 5′-di-tert-butylanilino) -1,
3,5-triazine, N, N'-hexamethylenebis-
(3,5-di-tert-butyl-4-hydroxyhydrocinnamide), N, N′-bis [3- (3,5-di-
tert-butyl-4-hydroxyphenyl) propionyl] hydrazine, 1,1,3-tris (2-methyl-
4-hydroxy-5-tert-butylphenyl) butane, 1,3,5-trimethyl-2,4,6-tris (3,5-di-tert-butyl-4-hydroxybenzyl) benzene, tris (3 5-di-tert-butyl-4-hydroxyphenyl) isocyanurate, tris (3,5-di-tert-butyl-4-hydroxybenzyl) isocyanurate, 1,3,5-tris (4-
tert-butyl-3-hydroxy-2,6-dimethylbenzyl) isocyanurate, 1,3,5-tris 2
[3 (3,5-di-tert-butyl-4-hydroxyphenyl) propionyloxy] ethyl isocyanurate, tetrakis [methylene-3- (3 ′, 5′-di-t)
tert-butyl-4-hydroxyphenyl) propionate] methane and the like. The composition ratio of these antioxidants is 0.0 to 100 parts by weight of the component A.
001 to 0.5 parts by weight are preferred.

For the purpose of improving weather resistance and cutting off harmful ultraviolet rays, an ultraviolet absorber or a light stabilizer is further added to the polycarbonate resin of either the component A or the component B of the present invention, particularly the polycarbonate resin of the component B. be able to. By using such a formulation, it is possible to use the layer B as the front side and achieve good weather resistance even in applications where transparency is important, such as glazing materials for vehicles, head lamps and turn signal materials, and the like. Becomes

Examples of the ultraviolet absorber include 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-n-octoxybenzophenone, 2-hydroxy-4-n-dodecyloxybenzophenone, 2-hydroxy-4-benzyloxybenzophenone, 2,2'-dihydroxy-4-
Methoxybenzophenone, 2-hydroxy-4-methoxy-2′-carboxybenzophenone, 2-hydroxy-4-methoxy-5-sulfoxybenzophenone, 2,
2'-dihydroxy-4,4'-dimethoxybenzophenone, 2,2 ', 4,4'-tetrahydroxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxy-5-sodiumsulfoxybenzophenone, bis (5
-Benzoyl-4-hydroxy-2-methoxyphenyl) methane and the like.

As the ultraviolet absorber, for example, 2-
(2′-hydroxy-5′-methylphenyl) benzotriazole, 2- (2′-hydroxy-5′-tert)
-Butylphenyl) benzotriazole, 2- (2'-
Hydroxy-5'-tert-octylphenyl) benzotriazole, 2- (2'-hydroxy-3 ', 5'
-Di-tert-butylphenyl) benzotriazole, 2- (2'-hydroxy-3 ', 5'-di-ter
t-amylphenyl) benzotriazole, 2- (2 ′
-Hydroxy-3'-dodecyl-5'-methylphenyl) benzotriazole, 2- (2'-hydroxy-
3 ′, 5′-bis (α, α′-dimethylbenzyl) phenylbenzotriazole, 2- [2′-hydroxy-
3 '-(3 ", 4", 5 ", 6" -tetraphthalimidomethyl) -5'-methylphenyl] benzotriazole, 2- (2'-hydroxy-3'-tert-butyl-5'-methylphenyl ) -5-chlorobenzotriazole, 2- (2′-hydroxy-3 ′, 5′-di-te)
rt-butylphenyl) -5-chlorobenzotriazole, 2,2 ′ methylenebis [4- (1,1,3,3-tetramethylbutyl) -6- (2H-benzotriazol-2-yl) phenol], methyl -3- [3-ter
Benzotriazole ultraviolet absorbers represented by condensates with t-butyl-5- (2H-benzotriazol-2-yl) -4-hydroxyphenylpropionate-polyethylene glycol can be mentioned.

Further, bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (1,2,2,2)
6,6-pentamethyl-4-piperidyl) sebacate,
Bis (1,2,2,6,6-pentamethyl-4-piperidyl) -2- (3,5-di-tert-butyl-4-hydroxybenzyl) -2n-butylmalonate,
Condensate of 2,3,4-butanecarboxylic acid with 2,2,6,6-tetramethyl-4-piperidinol and tridecyl alcohol, 1,2,3,4-butanedicarboxylic acid with 1,2,2 Condensation product of 6,6,6-pentamethyl-4-piperidinol and tridecyl alcohol, tetrakis (2,2,6,6-tetramethyl-4-piperidyl)-
1,2,3,4-butanetetracarboxylate, tetrakis (1,2,2,6,6-pentamethyl-4-piperidyl) -1,2,3,4-butanetetracarboxylate, poly {[6- (1,1,3,3-tetramethylbutyl) amino-1,3,5-triazine-2,4-diyl] [(2,2,6,6-tetramethylpiperidyl) imino] hexamethylene [(2 , 2,6,6-tetramethylpiperidyl) imino]}, poly {[6-morpholino-s-triazine-2,4-diyl] [(2,2,6
6-tetramethylpiperidyl) imino] hexamethylene [(2,2,6,6-tetramethylpiperidyl) imino]}, 1,2,3,4-butanetetracarboxylic acid and 2,2,6,6-tetra Methyl-4-piperidinol and β, β, β ′, β′-tetramethyl-3,9- (2,
Condensation product with 4,8,10-tetraoxaspiro [5,5] undecane) diethanol, N, N′-bis (3-aminopropyl) ethylenediamine and 2,4-bis [N-
Butyl-N- (1,2,2,6,6-pentamethyl-4
-Piperidyl) amino] -chloro-1,3,5-triazine, 1,2,3,4-butanetetracarboxylic acid, 1,2,2,6,6-pentamethyl-4-piperidinol and β , Β, β ', β'-tetramethyl-3,9
-(2,4,8,10-tetraoxaspiro [5,5]
A condensate with undecane) diethanol and a hindered amine-based light stabilizer represented by polymethylpropyl 3-oxy- [4- (2,2,6,6-tetramethyl) piperidinyl] siloxane can also be blended.

Further, a bluing agent can be added to the polycarbonate resin of the present invention in order to cancel a yellowish color due to an ultraviolet absorber or the like. As the bluing agent, any one can be used without any particular difficulty as long as it is used for a polycarbonate resin. Generally, anthraquinone dyes are easily available and preferred. As a specific bluing agent, for example, the common name Solven
t Violet 13 [CA. No. (color index No.) 60725; Trade name “Macrolex Violet B” manufactured by Bayer Corporation, “Diaresin Blue G” manufactured by Mitsubishi Chemical Corporation, “Sumiplast Violet B” manufactured by Sumitomo Chemical Co., Ltd.], general name Solvent Viol
et31 [CA. No. 68210; Trade name “Diaresin Violet D” manufactured by Mitsubishi Chemical Corporation], generic name S
Solvent Violet 33 [CA. No. 6072
5; trade name “Diaresin Blue J” manufactured by Mitsubishi Chemical Corporation], generic name Solvent Blue 94 [CA.
No. 61500; Trade name "Diaresin Blue N" manufactured by Mitsubishi Chemical Corporation], generic name Solvent Violet
t36 [CA. No. 68210; brand name “Macrolex Violet 3R” manufactured by Bayer AG], generic name Sol
vent Blue 97 [trade name “Macrolex Blue RR” manufactured by Bayer AG] and generic name Solvent
Blue 45 [CA. No. 61110; trade name "Tetrazol Blue RLS" manufactured by Sando Co., Ltd.] and Macrox Violet and Triazole Blue RLS manufactured by Ciba Specialty Chemicals Co., Ltd., and Macroxol Violet B and Triazole Blue RLS are particularly preferable.

In the resin of the present invention, small amounts of other conventional additives such as reinforcing agents (talc, mica, clay, wollastonite, calcium carbonate, glass fiber, glass beads, Glass balloon, milled fiber, glass flake, carbon fiber, carbon flake, carbon beads, carbon milled fiber, metal flake, metal fiber, metal coated glass fiber, metal coated carbon fiber, metal coated glass flake, silica, ceramic particles, ceramic fiber , Aramid particles, aramid fiber, polyarylate fiber, graphite, conductive carbon black, various whiskers, etc., flame retardant (halogen, phosphate ester, metal salt, red phosphorus, silicon, fluorine, metal hydration) Materials, etc.), heat-resistant agents, coloring agents (carbon black, Pigments such as titanium, dye),
Light diffusing agents (crosslinked acrylic particles, crosslinked silicon particles, ultra-thin glass flakes, calcium carbonate particles, etc.), fluorescent brighteners, luminous pigments, fluorescent dyes, antistatic agents, flow modifiers, nucleating agents, inorganic and organic Antibacterial agents, photocatalytic antifouling agents (fine particle titanium oxide, fine particle zinc oxide, etc.), impact modifiers represented by graft rubber, infrared absorbers, and photochromic agents.

In the present invention, by laminating the above-mentioned specific polycarbonate resin, it is possible to obtain a laminate having a small optical distortion and excellent in long-term properties such as wet heat resistance. It is suitable for applications that require high optical characteristics despite its large size and that are used for a long period of time under severe conditions.

[0093]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention and its effects will be described more specifically with reference to the following Examples and Comparative Examples, but the present invention is not limited by these Examples and the like.
The polycarbonate resin, protective film, and evaluation items used in Examples and Comparative Examples are shown below.

(Polycarbonate resin) (1) PC-1 From the intensity area ratio of the corresponding peak produced from bisphenol A and phosgene by an interfacial polycondensation method using an amine catalyst and measured using ¹ H-NMR. The required phenolic terminal group molar ratio was 1.2%, and Sandstab P-EPQ (Sands (San
(doz), a polycarbonate resin pellet having a viscosity average molecular weight of 18,500.

(2) PC-2 PC-2 is produced from bisphenol A similar to PC-1 and phosgene by an interfacial polycondensation method using an amine catalyst.
The molar ratio of the phenolic terminal group determined by the same method as in -1 was 9.4%, and Sandstab was used as a stabilizer.
P-EPQ (manufactured by Sandoz) was added to 0.
Having a viscosity average molecular weight of 18,500
Polycarbonate resin pellets.

(3) PC-3 The same phenolic terminal group as that of PC-1 was produced from bisphenol A and diphenyl carbonate by a melt polymerization method, and the molar ratio of the phenolic terminal group was 3 in the same manner as for PC-1.
8.6% and Sandstab P-
Polycarbonate resin pellets containing 0.03% by weight of EPQ (manufactured by Sandoz) and having a viscosity average molecular weight of 18,500.

(4) PC-4 The same phenolic terminal group as that of PC-1 was produced from the same bisphenol A and diphenyl carbonate by a melt polymerization method, and the molar ratio of the phenolic terminal groups was 3 in the same manner as for PC-1.
7.2% and Sandstab P- as a stabilizer
A polycarbonate resin containing 0.03% by weight of EPQ (manufactured by Sandoz) and having a viscosity average molecular weight of 22,500 was mixed under reduced pressure of 1330 Pa with 28
A polycarbonate resin sheet obtained by subjecting a 0.5 mm thick polycarbonate resin sheet obtained by melt extrusion using a T-die extruder having a gear pump at 0 ° C. to a silicon hard coat treatment shown below on one surface.

(5) PC-5 PC-5 is produced from bisphenol A similar to PC-1 and phosgene by an interfacial polycondensation method using an amine catalyst.
The molar ratio of the phenolic terminal group determined by the same method as that of -1 was 0.9%, and Sandstab was used as a stabilizer.
P-EPQ (manufactured by Sandoz) was added to 0.
Having a viscosity average molecular weight of 22,800
Polycarbonate resin powder of 1330 Pa
Polycarbonate resin sheet obtained by subjecting a 0.5 mm thick polycarbonate resin sheet obtained by melt extrusion using a T-die extruder having a gear pump at 280 ° C. under reduced pressure to a silicon hard coat treatment shown below on one surface. .

(Silicon Hard Coating Treatment) 70 parts of methyl methacrylate (hereinafter abbreviated as MMA) was placed in a nitrogen-purged flask equipped with a reflux condenser and a stirrer.
39 parts of hydroxyethyl methacrylate (hereinafter abbreviated as HEMA), azobisisobutyronitrile (hereinafter AI)
0.18 parts of BN) and 200 parts of 1,2-dimethoxyethane were added, mixed and dissolved. Then, the reaction was carried out in a nitrogen stream at 70 ° C. for 6 hours with stirring. The obtained reaction solution was added to n-hexane and purified by reprecipitation, and MMA / H
90 parts of an EMA copolymer (acrylic resin (I)) having a composition ratio of 70/30 (molar ratio) was obtained. The weight average molecular weight of the copolymer was measured by GPC (column; Shodex G).
PCA-804, eluent: THF) was 80,000 in terms of polystyrene.

Further, methyltrimethoxysilane 142
Parts, 72 parts of distilled water and 20 parts of acetic acid were mixed under cooling with ice water,
The mixture was stirred at 25 ° C. for 1 hour and diluted with 116 parts of isopropanol to obtain 350 parts of a solution (X) of a hydrolyzed condensate of methyltrimethoxysilane. On the other hand, 208 parts of tetraethoxysilane and 81 parts of 0.01 N hydrochloric acid are mixed under cooling with ice water, the mixture is stirred at 25 ° C. for 3 hours, diluted with 11 parts of isopropanol, and a solution of the hydrolyzed condensate of tetraethoxysilane ( Y) 300 parts were obtained.

Next, as the composition for the first layer of the hard coat,
8 parts of the acrylic resin (I) is methyl ethyl ketone 40
Parts, methyl isobutyl ketone 20 parts, ethanol 5.2
, 14 parts of isopropanol and 10 parts of 2-ethoxyethanol, and then dissolved in a solution of the hydrolyzed condensate of methyltrimethoxysilane (X).
10 parts were added and stirred at 25 ° C. for 5 minutes, and the solution was further added to a melamine resin (Cymel 3 manufactured by Mitsui Cytec Co., Ltd.).
03) 1 part was added and the mixture was stirred at 25 ° C for 5 minutes to prepare a coating composition (i).

Further, as a composition for the second layer of the hard coat,
Water-dispersed colloidal silica dispersion (Nissan Chemical Industries, Ltd.)
Made Snowtex 30 solid content concentration 30% by weight) 10
To 12 parts of distilled water and 20 parts of acetic acid were added and stirred.
4 parts were added. This mixture was stirred at 25 ° C. for 1 hour. To the reaction mixture obtained, 20 parts of a tetraethoxysilane hydrolyzed condensate solution (Y) and 1 part of sodium acetate as a curing catalyst were added, diluted with 200 parts of isopropanol, and coated. Composition (ii) was prepared.

The coating composition (i) was applied to one surface of a 0.5 mm thick polycarbonate resin sheet with a wire bar, allowed to stand at 25 ° C. for 20 minutes, and then thermally cured at 120 ° C. for 30 minutes. The thickness of the first layer was 2.5 μm. Next, the coating composition (ii) was further applied to the coating surface of the sheet with a wire bar, allowed to stand at 25 ° C for 20 minutes, and thermally cured at 120 ° C for 2 hours. The thickness of the second layer was 5.0 μm.

Protective Film A protective film having a pressure-sensitive adhesive layer of ethylene-vinyl acetate copolymer on a polyethylene substrate was used. The film thickness is 3
It was 5 μm.

Evaluation Items (1) Moisture and Heat Resistance The plate-shaped molded product was treated with an environmental tester (Platinous Subzero Lucifer manufactured by Tabai Espec Co., Ltd.) at 65 ° C. and 85% RH for 500 hours. Using a punch for punching with a semicircular tip and a radius of 1/4 inch, and a circular receiving table with a radius of 1/2 inch, in an atmosphere of 23 ° C. and 50% RH, with the sheet layer side of the upper side as the upper side, Using a high-speed surface impact tester (Hydroshot HTM-1 manufactured by Shimadzu Corporation) under the condition of a speed of 7 m / sec, the punch was made to collide with the central part of the substantially plate-shaped molded product, and the sample was made. The energy (J) required to cause breakthrough of the sample was measured, and a comparison with the impact strength before wet heat treatment was shown as the retention. Retention rate (%) = 100 × {(surface impact strength after long-term wet heat treatment) − (initial impact strength)} / (initial impact strength) A higher retention rate indicates better wet heat resistance.

(2) Optical distortion After the plate-like molded product was molded by 30 shots, the plate-like molded product was
The sheet was sandwiched between two orthogonal polarizing plates, and the distortion was visually observed. The evaluation was made based on the color change of the stripe pattern and the unevenness of the density, and the presence or absence of an uneven shaded portion. ：: No large distortion was observed, and there was no uneven shading. Δ: No large distortion is observed, but there is a case where an uneven shaded portion is observed. X: Large distortion is observed. The color change of the striped pattern is small, and the sparseness indicates that the optical distortion is small.

Example 1 The polycarbonate resin of the layer A was PC-1, and the polycarbonate resin was 120
After drying using a hot air dryer at 5 ° C. for 5 hours, molding was performed using an injection molding machine (SG260M-HP, manufactured by Sumitomo Heavy Industries, Ltd.) equipped with an injection device having a cylinder inner diameter of 45 mmφ.

Before filling with the resin, the polycarbonate resin sheet (PC-4: B layer) having a thickness of 500 μm and cut to the size on the surface of the mold core was previously adhered to the side in contact with the layer A and the opposite side. After removing the polyethylene protective film by hand, the resin sheet was attached by charging.

With the mold closed, a vacuum pump (combination of ULVAC PMB006CM mechanical booster manufactured by Nippon Vacuum Engineering Co., Ltd. and an EC 803 rotary pump) was used, followed by evacuation for 10 seconds, followed by molding. The evacuation was performed through a gas vent clearance provided around the mold cavity.

The molding conditions were as follows: a cylinder temperature of 300 ° C., a back pressure of 19.6 MPa, an injection speed of 70 mm / sec (first speed) at a constant injection speed, and a plate-like molded product. Such a molded product has a body length of 149 mm x a width of 152 m.
It is a plate-shaped molded product having a size of mx 5 mm and having a film-shaped gate (gate portion thickness 1.5 mm). The mold temperature was kept at 130 ° C. using a mold temperature controller.
The obtained molded article was evaluated as described above. As a result of the evaluation, even after the wet heat treatment, the surface impact strength retention rate was high, the optical distortion was small, and even after the formation of 30 shots, no uneven shading was observed at all. Table 1 shows the evaluation results.

Example 2 A plate-like molded product was obtained in the same manner as in Example 1 except that the polycarbonate resin of the layer A was PC-2. The same evaluation as in Example 1 was performed on the obtained molded product. As a result of the evaluation, the retention rate of the surface impact strength was slightly reduced as compared with Example 1, but was 80%.
, Less optical distortion and no uneven shading. Table 1 shows the evaluation results.

Comparative Example 1 A plate-like molded product was obtained in the same manner as in Example 1, except that the polycarbonate resin for the layer A was PC-3. The same evaluation as in Example 1 was performed on the obtained molded product. As a result of the evaluation, optical distortion and uneven shading did not occur, but the surface impact strength was significantly reduced. Table 1 shows the evaluation results.

Comparative Example 2 A plate-like molded product was obtained in the same manner as in Example 1, except that the polycarbonate resin in the layer A was PC-1 and the polycarbonate resin in the layer B was PC-5. . The same evaluation as in Example 1 was performed on the obtained molded product. As a result of the evaluation, the retention of surface impact strength was high and no large optical distortion was observed, but many nonuniform shadows were generated. Table 1 shows the evaluation results.

[0114]

[Table 1]

[0115]

According to the present invention, it is possible to obtain a laminate of a polycarbonate resin which has a low distortion, has few molding defects, and has excellent long-term strength characteristics. Such a laminate can provide a molded article having a small distortion and a high design property in various fields such as a building, a vehicle, an electric / electronic device, a machine, and the like, and thus has an extremely large industrial effect. .

Claims (5)

[Claims] 1. A laminate comprising a plurality of layers made of polycarbonate resin substantially in contact with each other, wherein one layer (A
Layer) is 100% by mole of the total of the phenolic end groups and the non-phenolic end groups, and the amount (x) of the phenolic end groups is 2
The other layer (layer B) is composed of less than 0 mol% of the polycarbonate resin (component A), and the other layer (layer B) has an amount of phenolic terminal group (y ) Comprises 5 to 80 mol% of a polycarbonate resin (component (B)). 2. The polycarbonate resin laminate according to claim 1, wherein x is less than 10 mol% and y is 10 to 65 mol%. 3. The polycarbonate resin laminate according to claim 1, wherein x is less than 10 mol% and y is 20 to 60 mol%. 4. A component is insert-injection-molded into a mold cavity into which a molded body for forming a layer B is inserted.
The polycarbonate resin laminate according to any one of claims 1 to 3, wherein a layer is formed. 5. The molded product forming the layer B is at least A
The polycarbonate resin laminate according to any one of claims 1 to 4, wherein the surface in contact with the layer is protected by a protective film, and after removing the protective film, a laminate with the layer A is formed. body.