JP2021134349A - Sheet or film, and laminate - Google Patents

Abstract

To provide a sheet or a film, and a laminate with excellent transparency, acid resistance, chemical resistance, surface hardness, bendability and adhesion.SOLUTION: A sheet or film is formed from a resin composition that contains a polycarbonate resin (A) containing a unit (a) represented by formula (1) of 5-85 mol%, a unit (b) represented by formula (2) of 15-95 mol%, and a carbonate unit (c) different from (a) and (b) of 0-80 mol% and a polycarbonate resin (B) containing the unit (a) of less than 5 mol%, the unit (b) of 30-100 mol%, and the unit (c) of 0-70 mol%.SELECTED DRAWING: None

Description

The present invention relates to a polycarbonate sheet or film having excellent transparency, acid resistance, chemical resistance, surface hardness, flexibility, and adhesion, and a laminate.

Conventionally, as a transparent resin, a methacrylic resin, a polycarbonate resin composed of bisphenol A (hereinafter, may be referred to as PC-A) and the like are known, and electric / electronic parts, optical parts, automobiles, etc. in the form of molded products, films, etc. It is used in a wide range of fields such as parts and machine parts.

Methacrylic acid resins such as polymethylmethacrylate (hereinafter sometimes referred to as PMMA) have high transparency and hard surface hardness (pencil hardness H to 3H), and are often used as optical materials for lenses, optical fibers, and the like. .. However, there is a problem that the resistance to daily chemicals such as sunscreen is low, and the use in applications where human hands directly touch is restricted. Non-Patent Document 1 describes that acrylic resin has a problem of resistance to fragrances and sunburn creams.

In recent years, due to concerns about the depletion of petroleum resources and the problem of an increase in carbon dioxide in the air that causes global warming, carbon neutrality has been established that does not depend on oil for raw materials and does not increase carbon dioxide even when burned. Biomass resources have attracted a great deal of attention, and in the field of polymers, biomass plastics produced from biomass resources are being actively developed. In particular, polycarbonate, which mainly uses isosorbide as a monomer, is excellent in heat resistance, weather resistance, surface hardness, and chemical resistance, and has been attracting attention because it has different characteristics from PC-A, and various studies have been conducted. (Patent Documents 1 and 2). While these isosorbide-based polycarbonates are excellent in heat resistance, impact resistance, and weather resistance, their adhesion to other resins, such as PC-A and PMMA, is extremely poor, and it is usually difficult to form a laminate. there were. In addition, the vulnerability to chemicals such as acids and sunscreen creams has become apparent.

So far, there are still sheets or films that have excellent transparency, chemical resistance, surface hardness, and flexibility, and have excellent adhesion to various thermoplastic resins, using a resin that is a mixture of two or more isosorbide-based polycarbonates. It was not provided.

Japanese Unexamined Patent Publication No. 2006-36954 JP-A-2009-46519

"2013 Decorative Film-related Market Outlook and Manufacturer Strategy" pp. 118-122 Fuji Keizai

An object of the present invention is to provide a polycarbonate sheet or film having excellent transparency, acid resistance, chemical resistance, surface hardness, flexibility and adhesion, and a laminate.

As a result of intensive studies, the present inventors have conducted a polycarbonate resin (A) containing a certain ratio of a monomer having a specific spiro ring structure and a monomer having a specific hetero ring structure, and a monomer having a specific hetero ring structure. By using a resin composition containing a polycarbonate resin (B) containing a certain ratio or more of the above, and optionally an acrylic resin, the resin composition is excellent in transparency, acid resistance, chemical resistance, surface hardness, and flexibility. , It has been investigated that the adhesion with other thermoplastic resins can be improved, and the present invention has been completed.

That is, according to the present invention, the subject of the invention is achieved by the following paragraphs 1 to 13.

1. 1. The repeating unit is from the unit (a) represented by the following formula (1), the unit (b) represented by the following formula (2), and the carbonate unit (c) other than the unit (a) and the unit (b). The repeating unit is the polycarbonate resin (A) containing 5 to 85 mol% of the unit (a), 15 to 95 mol% of the unit (b), and 0 to 80 mol% of the unit (c) among all the repeating units. It consists of a unit (a) represented by the following formula (1), a unit (b) represented by the following formula (2), and a carbonate unit (c) other than the unit (a) and the unit (b). Formed from a resin composition containing a polycarbonate resin (B) containing less than 5 mol% of the unit (a), 30 to 100 mol% of the unit (b), and 0 to 70 mol% of the unit (c) in the repeating unit. Sheet or film.

(In the formula, W represents an alkylene group having 1 to 20 carbon atoms or a cycloalkylene group having 6 to 20 carbon atoms, and R has a branched or linear alkyl group having 1 to 20 carbon atoms or a substituent. It represents a cycloalkyl group having 6 to 20 carbon atoms, and m represents an integer of 0 to 10.)

2. The sheet or film according to item 1 above, wherein the weight ratio of the polycarbonate resin (A) to the polycarbonate resin (B) is 5:95 to 95: 5.
3. 3. The sheet or film according to item 1 or 2 above, wherein the resin composition further contains an acrylic resin (C).
4. The sheet or film according to item 3 above, wherein the weight ratio of the total of the polycarbonate resin (A) and the polycarbonate resin (B) to the acrylic resin (C) is 10:90 to 90:10.
5. The sheet or film according to any one of the above items 1 to 4, wherein the haze is 2.5% or less.
6. The sheet or film according to any one of the above items 1 to 5, which has a thickness of 30 μm or more and 500 μm or less.

7. A laminate formed from a sheet layer formed of a thermoplastic resin (D) and a film layer formed on at least one side of the sheet layer, and the repeating unit of the film layer is represented by the following formula (1). It is composed of a unit (a) to be formed, a unit (b) represented by the following formula (2), and a carbonate unit (c) other than the unit (a) and the unit (b). ) Is 5 to 85 mol%, the unit (b) is 15 to 95 mol%, the unit (c) is 0 to 80 mol%, and the repeating unit is represented by the following formula (1). It consists of (a), a unit (b) represented by the following formula (2), and a carbonate unit (c) other than the unit (a) and the unit (b), and the unit (a) is 5 among all repeating units. A laminate which is a film layer formed from a resin composition containing less than mol%, a polycarbonate resin (B) containing 30 to 100 mol% of the unit (b), and 0 to 70 mol% of the unit (c).

(In the formula, W represents an alkylene group having 1 to 20 carbon atoms or a cycloalkylene group having 6 to 20 carbon atoms, and R has a branched or linear alkyl group having 1 to 20 carbon atoms or a substituent. It represents a cycloalkyl group having 6 to 20 carbon atoms, and m represents an integer of 0 to 10.)

8. The laminate according to item 7 above, wherein the weight ratio of the polycarbonate resin (A) to the polycarbonate resin (B) is 5:95 to 95: 5.
9. The laminate according to item 7 or 8 above, wherein the resin composition contains an acrylic resin (C).
10. The laminate according to item 9, wherein the weight ratio of the total of the polycarbonate resin (A) and the polycarbonate resin (B) to the acrylic resin (C) is 10:90 to 90:10.
11. The laminate according to any one of items 7 to 10 above, wherein the haze is 2.5% or less.
12. The laminate according to any one of items 7 to 11 above, wherein the thickness of the film layer is 25 μm or more and 250 μm or less.
13. The laminate according to any one of items 7 to 12 above, wherein the thickness of the sheet layer is 100 μm or more and 500 μm or less.

The present invention relates to a polycarbonate resin (A) containing a certain ratio of a monomer having a specific spiro ring structure and a monomer having a specific hetero ring structure, and a polycarbonate resin containing a certain ratio or more of a monomer having a specific hetero ring structure ( By using a resin composition containing B) and, if desired, an acrylic resin, a sheet or film formed from the resin composition, a layer made of the resin composition, and another thermoplastic resin can be used. It has become possible to provide a product having excellent transparency, acid resistance, chemical resistance, surface hardness, flexibility, and adhesion of the laminated body having the above-mentioned layer. Therefore, the industrial effect it produces is exceptional.

Hereinafter, the present invention will be described in detail.

(Aspect 1 of the present invention)
In the present invention, the repeating unit is a unit (a) represented by the following formula (1), a unit (b) represented by the following formula (2), and a carbonate unit other than the unit (a) and the unit (b) ( c), and the polycarbonate resin (A) containing 5 to 85 mol% of the unit (a), 15 to 95 mol% of the unit (b), and 0 to 80 mol% of the unit (c) in all the repeating units. , The repeating unit is the unit (a) represented by the following formula (1), the unit (b) represented by the following formula (2), and the carbonate unit (c) other than the unit (a) and the unit (b). A resin comprising a polycarbonate resin (B) containing less than 5 mol% of the unit (a), 30 to 100 mol% of the unit (b), and 0 to 70 mol% of the unit (c) in all the repeating units. A sheet or film formed from the composition.

(In the formula, W represents an alkylene group having 1 to 20 carbon atoms or a cycloalkylene group having 6 to 20 carbon atoms, and R has a branched or linear alkyl group having 1 to 20 carbon atoms or a substituent. It represents a cycloalkyl group having 6 to 20 carbon atoms, and m represents an integer of 0 to 10.)

(Polycarbonate resin (A))
In the polycarbonate resin (A) used in the present invention, the repeating unit is the unit (a) represented by the formula (1), the unit (b) represented by the formula (2), and the unit (a) and the unit. It consists of a carbonate unit (c) other than (b), and the unit (a) is 5 to 85 mol%, the unit (b) is 15 to 95 mol%, and the unit (c) is 0 to 80 mol% in all the repeating units. % Is contained in the polycarbonate resin (A).

The unit (a) represented by the above formula (1) is derived from a diol having a specific spiro ring structure. Examples of the diol compound having such a spiro ring structure include 3,9-bis (2-hydroxyethyl) -2,4,8,10-tetraoxaspiro (5.5) undecane and 3,9-bis (2-hydroxy-). 1,1-Dimethylethyl) -2,4,8,10-tetraoxaspiro (5.5) undecane, 3,9-bis (2-hydroxy-1,1-diethylethyl) -2,4,8, 10-Tetraoxaspiro (5.5) undecane, 3,9-bis (2-hydroxy-1,1-dipropylethyl) -2,4,8,10-tetraoxaspiro (5.5) undecane, etc. An alicyclic diol compound can be mentioned.

Preferably, 3,9-bis (2-hydroxy-1,1-dimethylethyl) -2,4,8,10-tetraoxaspiro (5.5) undecane is used.

The polycarbonate resin (A) used in the resin composition in the present invention contains 5 to 85 mol% of the unit (a) represented by the above formula (1) in the repeating unit, and 10 to 80 mol%. It is preferably contained, more preferably 15 to 70 mol%, further preferably 20 to 60 mol%, and particularly preferably 20 to 50 mol%. When the unit (a) is within the above range, the sheet or film formed from the resin composition blended with the polycarbonate resin (B) has an excellent balance of transparency, acid resistance, chemical resistance, surface hardness, and flexibility. .. Further, it is preferable that the polycarbonate resin is easily polymerized without crystallizing during the polymerization. Further, when the acrylic resin (C) is used, it is preferable that the resin composition with the acrylic resin does not become cloudy due to phase separation during extrusion or molding.

The unit (b) represented by the above formula (2) is derived from a diol having a specific ether group (having a heterocyclic structure). Examples of such diols include units (b-1), (b-2) and (b-3) represented by the following formulas having a stereoisomeric relationship.

These are sugar-derived ether diols, which are also obtained from natural biomass, and are one of the so-called renewable resources. The repeating units (b-1), (b-2) and (b-3) are called isosorbide, isomannide and isoidide, respectively. Isosorbide is obtained by hydrogenating D-glucose obtained from starch and then dehydrating it. Other ether diols can be obtained by the same reaction except for the starting material.

Among isosorbide, isomannide, and isosorbide, the repeating unit derived from isosorbide (1,4; 3,6-dianhydro-D-sorbitol) is particularly preferable because it is easy to manufacture and has excellent heat resistance.

The polycarbonate resin (A) used in the resin composition in the present invention contains 15 to 95 mol% of the unit (b) represented by the above formula (2) as a repeating unit in 20 to 90 mol%. It is preferably contained, more preferably 30 to 85 mol%, further preferably 40 to 80 mol%, and particularly preferably 50 to 80 mol%. When the unit (b) is within the above range, the sheet or film formed from the resin composition blended with the polycarbonate resin (B) has an excellent balance of transparency, acid resistance, chemical resistance, surface hardness and flexibility. ..

The polycarbonate resin (A) used in the resin composition in the present invention can contain a carbonate unit (c) other than the unit (a) and the unit (b).

The carbonate unit (c) is preferably a carbonate unit (c) derived from at least one compound selected from the group consisting of an aliphatic diol compound, an alicyclic diol compound and an aromatic dihydroxy compound. The carbonate unit (c) is a carbonate unit (c) derived from at least one compound selected from the group consisting of an aliphatic diol compound and an alicyclic diol compound in terms of surface hardness and weather resistance. Is preferable.

Examples of the aliphatic diol compound include 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,8-octanediol, 1.9-nonanediol, and 1, , 10-decanediol, 1,12-dodecanediol, 2-methyl-1,3-propanediol, neopentyl glycol, 3-methyl-1,5-pentanediol, 2-n-butyl-2-ethyl-1 , 3-Propanediol, 2,2-diethyl-1,3-propanediol, 2,4-diethyl-1,5-pentanediol, 1,2-hexaneglycol, 1,2-octylglycol, 2-ethyl- Examples include 1,3-hexanediol, 2,3-diisobutyl-1,3-propanediol, 2,2-diisoamyl-1,3-propanediol, 2-methyl-2-propyl-1,3-propanediol and the like. Therefore, 1,8-octanediol, 1.9-nonanediol, 1,10-decanediol, and 1,12-dodecanediol are preferably used.

Examples of the alicyclic diol compound include cyclohexanediols such as 1,2-cyclohexanediol, 1,3-cyclohexanediol, 1,4-cyclohexanediol, 2-methyl-1,4-cyclohexanediol, and 1,2-cyclohexane. Cyclohexanedimethanol such as dimethanol, 1,3-cyclohexanedimethanol, 1,4-cyclohexanedimethanol, norbornanedimethanol such as 2,3-norbornanedimethanol, 2,5-norbornanedimethanol, tricyclode Examples thereof include candimethanol, pentacyclopentadecanedimethanol, 1,3-adamantandiol, 2,2-adamantandiol, decalingdimethanol, 2,2,4,4-tetramethyl-1,3-cyclobutanediol, and the like. Cyclohexanedimethanols are preferably used.

Examples of the aromatic dihydroxy compound include α, α'-bis (4-hydroxyphenyl) -m-diisopropylbenzene (bisphenol M), 9,9-bis (4-hydroxy-3-methylphenyl) fluorene, and 1,1-. Bis (4-hydroxyphenyl) cyclohexane, 1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane, 4,4'-dihydroxy-3,3'-dimethyldiphenylsulfide, bisphenol A, 2 , 2-bis (4-hydroxy-3-methylphenyl) propane (bisphenol C), 2,2-bis (4-hydroxyphenyl) -1,1,1,3,3,3-hexafluoropropane (bisphenol AF) ), 1,1-Bis (4-hydroxyphenyl) decane and the like, and bisphenol A is preferably used.

The polycarbonate resin (A) used in the resin composition of the present invention preferably contains 1 to 60 mol%, preferably 1 to 60 mol%, and 2 to 40 of the repeating unit containing the carbonate unit (c) in the total repeating unit. It is more preferably contained in mol%, further preferably contained in an amount of 3 to 20 mol%, and particularly preferably contained in an amount of 4 to 10 mol%. When the unit (c) is within the above range, the sheet or film formed from the resin composition blended with the polycarbonate resin (B) has an excellent balance of transparency, acid resistance, chemical resistance, surface hardness and flexibility. ..

(Polycarbonate resin (B))
The polycarbonate resin (B) used in the resin composition in the present invention has a repeating unit represented by the following formula (1), a unit (a), a unit (b) represented by the following formula (2), and a unit ( It consists of a carbonate unit (c) other than a) and the unit (b), and the unit (a) is less than 5 mol% and contains 30 to 100 mol% of the unit (b) in all repeating units, and the unit (c). ) Is a polycarbonate resin containing 0 to 70 mol%.

(In the formula, W represents an alkylene group having 1 to 20 carbon atoms or a cycloalkylene group having 6 to 20 carbon atoms, and R has a branched or linear alkyl group having 1 to 20 carbon atoms or a substituent. It represents a cycloalkyl group having 6 to 20 carbon atoms, and m represents an integer of 0 to 10.)

The unit (a) represented by the above formula (1) is derived from a diol having a specific spiro ring structure. Examples of the diol compound having such a spiro ring structure include the same compounds as those described above.

In the polycarbonate resin (B) used in the resin composition in the present invention, the repeating unit of the unit (a) represented by the above formula (1) is less than 5 mol% in all repeating units, and 3 mol% or less. It is preferably 1 mol% or less, and it is particularly preferable that the unit (a) is not substantially contained. When the unit (a) is within the above range, the sheet or film formed from the resin composition blended with the polycarbonate resin (A) has an excellent balance of transparency, acid resistance, chemical resistance, surface hardness, and flexibility. ..

The unit (b) represented by the above formula (2) is derived from a diol having a specific ether group (having a heterocyclic structure). Examples of such diols are the same as those of the above-mentioned compounds.

The polycarbonate resin (B) used in the resin composition in the present invention contains 30 to 100 mol% of the unit (b) represented by the above formula (2) in the repeating unit, and 50 to 99 mol%. It is preferably contained, more preferably 60 to 98 mol%, further preferably 70 to 97 mol%, and particularly preferably 80 to 96 mol%. When the unit (b) is within the above range, the sheet or film formed from the resin composition blended with the polycarbonate resin (A) has an excellent balance of transparency, acid resistance, chemical resistance, surface hardness, and flexibility. ..

The polycarbonate resin (B) used in the resin composition in the present invention can contain a carbonate unit (c) other than the unit (a) and the unit (b).

The carbonate unit (c) is preferably a carbonate unit (c) derived from at least one compound selected from the group consisting of an aliphatic diol compound, an alicyclic diol compound and an aromatic dihydroxy compound. The carbonate unit (c) is a carbonate unit (c) derived from at least one compound selected from the group consisting of an aliphatic diol compound and an alicyclic diol compound in terms of surface hardness and weather resistance. Is preferable.

Examples of the aliphatic diol compound, the alicyclic diol compound and the aromatic dihydroxy compound include the same compounds as those described above.

The polycarbonate resin (B) used in the resin composition of the present invention preferably contains 0 to 70 mol%, preferably 1 to 50 mol%, preferably 2 to 40 mol% of the carbonate unit (c) in the total repeating unit. It is more preferably contained in mol%, further preferably contained in an amount of 3 to 30 mol%, and particularly preferably contained in an amount of 4 to 20 mol%. When the unit (c) is within the above range, the sheet or film formed from the resin composition blended with the polycarbonate resin (A) has an excellent balance of transparency, acid resistance, chemical resistance, surface hardness, and flexibility. ..

(Manufacturing method of polycarbonate resin)
The polycarbonate resin of the polycarbonate resin (A) and the polycarbonate resin (B) used in the present invention reacts a carbonate precursor such as a carbonic acid diester with a reaction means known per se for producing an ordinary polycarbonate resin, for example, a diol component. Manufactured by the method. Next, the basic means for these manufacturing methods will be briefly described.

The transesterification reaction using a carbonic acid diester as a carbonic acid precursor is carried out by a method in which a predetermined proportion of the diol component is stirred with the carbonic acid diester while heating under an inert gas atmosphere to distill off the produced alcohol or phenols. The reaction temperature varies depending on the boiling point of the alcohol or phenol produced, but is usually in the range of 120 to 300 ° C. The reaction is completed by distilling off the produced alcohols or phenols under reduced pressure from the initial stage. Further, if necessary, a terminal terminator, an antioxidant or the like may be added.

Examples of the carbonic acid diester used in the transesterification reaction include esters such as an aryl group having 6 to 12 carbon atoms and an aralkyl group which may be substituted. Specific examples thereof include diphenyl carbonate, ditriel carbonate, bis (chlorophenyl) carbonate and m-cresyl carbonate. Of these, diphenyl carbonate is particularly preferable. The amount of the diphenyl carbonate used is preferably 0.97 to 1.10 mol, more preferably 1.00 to 1.06 mol, based on 1 mol of the total dihydroxy compound.

Further, in the melt polymerization method, a polymerization catalyst can be used in order to increase the polymerization rate, and examples of such a polymerization catalyst include alkali metal compounds, alkaline earth metal compounds, nitrogen-containing compounds, and metal compounds.

As such a compound, an organic acid salt, an inorganic salt, an oxide, a hydroxide, a hydride, an alkoxide, a quaternary ammonium hydroxide, or the like of an alkali metal or an alkaline earth metal is preferably used, and these compounds are used. It can be used alone or in combination.

Examples of alkali metal compounds include sodium hydroxide, potassium hydroxide, cesium hydroxide, lithium hydroxide, sodium hydrogencarbonate, sodium carbonate, potassium carbonate, cesium carbonate, lithium carbonate, sodium acetate, potassium acetate, cesium acetate, lithium acetate, etc. Sodium stearate, potassium stearate, cesium stearate, lithium stearate, sodium boron hydride, sodium benzoate, potassium benzoate, cesium benzoate, lithium benzoate, disodium hydrogen phosphate, dipotassium hydrogen phosphate, phosphorus Examples thereof include 2 lithium hydrogen acid, 2 sodium phenyl phosphate, 2 sodium salt of bisphenol A, 2 potassium salt, 2 cesium salt, 2 lithium salt, sodium phenol salt, potassium salt, cesium salt, lithium salt and the like.

Examples of alkaline earth metal compounds include magnesium hydroxide, calcium hydroxide, strontium hydroxide, strontium hydroxide, magnesium carbonate, calcium carbonate, strontium carbonate, barium carbonate, magnesium diacetate, calcium diacetate, strontium diacetate, and diacetic acid. Examples thereof include barium and barium stearate.

Examples of the nitrogen-containing compound include quaternary ammonium hydroxides having alkyl and aryl groups such as tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide and trimethylbenzylammonium hydroxide. Can be mentioned. Examples thereof include tertiary amines such as triethylamine, dimethylbenzylamine and triphenylamine, and imidazoles such as 2-methylimidazole, 2-phenylimidazole and benzimidazole. Further, bases or basic salts such as ammonia, tetramethylammonium borohydride, tetrabutylammonium borohydride, tetrabutylammoniumtetraphenylborate, tetraphenylammoniumtetraphenylborate and the like are exemplified.

Examples of the metal compound include zinc aluminum compounds, germanium compounds, organotin compounds, antimony compounds, manganese compounds, titanium compounds, zirconium compounds and the like. These compounds may be used alone or in combination of two or more.

The amount of these polymerization catalysts used is preferably 1 × 10 ^-9 to 1 × 10 ⁻² equivalents, preferably 1 × 10 ^-8 to 1 × 10 ⁻⁵ equivalents, and more preferably 1 × 10 to 1 mol of the diol component. It is selected in the range of ^10-7 to 1 × 10 ^{-3 equivalents.}

It is also possible to add a catalytic deactivator in the latter stage of the reaction. As the catalyst deactivating agent to be used, known catalyst deactivating agents are effectively used, and among these, ammonium salts and phosphonium salts of sulfonic acids are preferable. Further, salts of dodecylbenzenesulfonic acid such as tetrabutylphosphonium salt of dodecylbenzenesulfonic acid and salts of paratoluenesulfonic acid such as paratoluenesulfonic acid tetrabutylammonium salt are preferable.

As esters of sulfonic acid, methyl benzenesulfonate, ethyl benzenesulfonate, butyl benzenesulfonate, octyl benzenesulfonate, phenylbenzenesulfonate, methyl paratoluenesulfonate, ethyl paratoluenesulfonate, butyl paratoluenesulfonate, Octyl paratoluene sulfonate, phenyl paratoluene sulfonate and the like are preferably used. Of these, the tetrabutylphosphonium salt of dodecylbenzenesulfonic acid is most preferably used.

The amount of these catalyst deactivators used is preferably 0.5 to 50 mol per mole of the catalyst when at least one polymerization catalyst selected from the alkali metal compound and / or the alkaline earth metal compound is used. It can be used in proportions, more preferably 0.5 to 10 mol, and even more preferably 0.8 to 5 mol.

(Specific viscosity: η _SP )
_{The specific viscosity (η SP} ) of the polycarbonate resin (A) and the polycarbonate resin (B) is preferably in the range of 0.2 to 1.5. When the specific viscosity is in the range of 0.2 to 1.5, the strength and moldability of the molded product such as a film are good. It is more preferably 0.25 to 1.2, still more preferably 0.3 to 1.0, and particularly preferably 0.3 to 0.5.

The specific viscosity referred to in the present invention is determined from a solution prepared by dissolving 0.7 g of a polycarbonate resin in 100 ml of methylene chloride at 20 ° C. using an Ostwald viscometer.
Specific viscosity (η _SP ) = (t-t ₀ ) / t ₀
[T ₀ is the number of seconds for methylene chloride to fall, t is the number of seconds for the sample solution to fall]
The specific specific viscosity can be measured, for example, as follows. First, the polycarbonate resin is dissolved in 20 to 30 times the weight of methylene chloride, and the soluble component is collected by Celite filtration, and then the solution is removed and sufficiently dried to obtain a solid of methylene chloride soluble component. The specific viscosity at 20 ° C. of a solution prepared by dissolving 0.7 g of such a solid in 100 ml of methylene chloride is determined using an Ostwald viscometer.

(Acrylic resin (C))
In the present invention, the resin composition can further contain an acrylic resin (C). A sheet or film formed from a resin composition containing an acrylic resin (C) is excellent in a balance of transparency, acid resistance, chemical resistance, surface hardness, and flexibility.

As the acrylic resin used in the resin composition in the present invention, known ones can be used. For example, the following compounds can be mentioned as monomers used for acrylic resins. Methyl methacrylate, methacrylic acid, acrylic acid, benzyl (meth) acrylate, n-butyl (meth) acrylate, i-butyl (meth) acrylate, t-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl ( Meta) acrylate, tridecyl (meth) acrylate, stearyl (meth) acrylate, glycidyl (meth) acrylate, hydroxypropyl (meth) acrylate, 2-methoxyethyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, cyclohexyl (meth) ) Acrylate, isobornyl (meth) acrylate, norbornyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, Acrylate (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2- (meth) acroyloxyethyl succinate, 2- (meth) acroyloxyethyl maleate, 2- (meth) acroyloxyethyl phthalate , Hexahydrophthalic acid 2- (meth) acrylic oil oxyethyl, pentamethylpiperidyl (meth) acrylate, tetramethylpiperidyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, cyclopentyl methacrylate, cyclopentyl Examples thereof include acrylate, cyclohexyl methacrylate, cyclohexyl acrylate, cycloheptyl methacrylate, cycloheptyl acrylate, cyclooctyl methacrylate, cyclooctyl acrylate, cyclododecyl methacrylate, and cyclododecyl acrylate. These may be polymerized alone or may be used by polymerizing two or more kinds.

In particular, it is preferable to contain methyl methacrylate and methyl acrylate. As the monomer component, it is preferable to contain 50 to 99 mol% of methyl methacrylate and 1 to 50 mol% of methyl acrylate, and more preferably 60 to 99 mol% of methyl methacrylate and 1 to 40 mol% of methyl acrylate. It is even more preferable to contain 70 to 99 mol% of methyl acrylate and 1 to 30 mol% of methyl acrylate. When methyl methacrylate is more than 99 mol% as the monomer component, the heat-decomposability is inferior, and molding defects such as silver may occur during molding. When methyl methacrylate is less than 50 mol% as the monomer component, the thermal deformation temperature may decrease.

(Manufacturing method of resin composition containing polycarbonate resin and acrylic resin)
The resin composition in the present invention is preferably a blend of a polycarbonate resin (A), a polycarbonate resin (B), and optionally an acrylic resin (C) in a molten state. As a method of blending in a molten state, an extruder is generally used, and the molten resin is kneaded and pelletized at a molten resin temperature of 200 to 320 ° C., preferably 220 to 300 ° C., more preferably 230 to 290 ° C. As a result, pellets of a resin composition in which both resins are uniformly blended can be obtained. The configuration of the extruder, the configuration of the screw, and the like are not particularly limited. If the temperature of the molten resin in the extruder exceeds 320 ° C, the resin may be colored or thermally decomposed. On the other hand, if the resin temperature is lower than 200 ° C., the resin viscosity may be too high and the extruder may be overloaded.

(Weight ratio)
The weight ratio of the polycarbonate resin (A) and the polycarbonate resin (B) can be arbitrarily mixed. It is preferably in the range of 5:95 to 95: 5 (weight ratio), more preferably in the range of 10:90 to 90:10 (weight ratio), and even more preferably in the range of 20:80 to 85:15 (weight ratio). ), Especially preferably in the range of 30:70 to 80:20 (weight ratio), and most preferably in the range of 40:60 to 80:20 (weight ratio). If the content of the polycarbonate resin (A) is less than 5% by weight, the transparency and surface hardness may be lowered, and if it exceeds 95% by weight, the acid resistance, chemical resistance and surface hardness may be lowered.

The weight ratio of the mixture of the polycarbonate resin (A) and the polycarbonate resin (B) to the acrylic resin (C) can be arbitrarily mixed. It is preferably in the range of 10:90 to 90:10 (weight ratio), more preferably in the range of 20:80 to 80:20 (weight ratio), and even more preferably in the range of 30:70 to 70:30 (weight ratio). Yes, particularly preferably in the range of 40:60 to 65:35 (weight ratio), and most preferably in the range of 50:50 to 60:40 (weight ratio). If the polycarbonate component is less than 5% by weight, acid resistance, chemical resistance, and flexibility may be inferior. Further, if the acrylic component is less than 5% by weight, the surface hardness may be inferior. Within the above range, a resin composition having excellent transparency, heat resistance, acid resistance, chemical resistance, surface hardness, flexibility, and adhesion to other thermoplastic resins can be obtained.

(Glass transition temperature: Tg)
The glass transition temperature (Tg) of the resin composition in the present invention is single, and the glass transition temperature (Tg) is preferably 90 to 150 ° C, more preferably 100 to 140 ° C, still more preferably 110. ~ 130 ° C. When Tg is within the above range, heat resistance stability and moldability are good, which is preferable.

The glass transition temperature (Tg) is measured using a 2910 type DSC manufactured by TA Instruments Japan Co., Ltd. at a heating rate of 20 ° C./min. In the present invention, the single glass transition temperature (Tg) means that the glass transition temperature is measured using a differential scanning calorimeter (DSC) at a heating rate of 20 ° C./min according to JIS K7121. Only one inflection point indicating the glass transition temperature appears.

In general, a single glass transition temperature in a polymer blend composition means that the resins to be mixed are in a state of being compatible with each other on the nanometer order (molecular level). Can be admitted.

(Pencil hardness)
The resin composition in the present invention preferably has a pencil hardness of HB or higher, and more preferably F or higher. It is more preferably H or higher in terms of excellent scratch resistance. The pencil hardness of 4H or less has a sufficient function. Pencil hardness can be increased by increasing the weight ratio of the acrylic resin. In the present invention, the pencil hardness is a hardness that does not leave scratch marks even when the resin of the present invention is rubbed with a pencil having a specific pencil hardness, and is measured according to JIS K-5600. It is preferable to use the pencil hardness used for the surface hardness test of the resulting coating film as an index. Pencil hardness is 9H, 8H, 7H, 6H, 5H, 4H, 3H, 2H, H, F, HB, B, 2B, 3B, 4B, 5B, 6B, and the hardest is 9H, the hardest. The soft one is 6B.

(Additive)
The resin composition used in the present invention is a heat stabilizer, a plasticizer, a light stabilizer, a polymer metal inactivating agent, a flame retardant, a lubricant, an antistatic agent, a surfactant, and an antibacterial agent, depending on the application and need. , UV absorbers, mold release agents, colorants, impact modifiers and other additives can be added.

(Heat stabilizer)
The resin composition used in the present invention preferably contains a heat stabilizer in order to suppress a decrease in molecular weight and deterioration of hue during extrusion and molding. Examples of the heat stabilizer include phosphorus-based heat stabilizers, phenol-based heat stabilizers, and sulfur-based heat stabilizers, and one of these can be used alone or in combination of two or more. In particular, since the ether diol residue of the unit (a-1) is deteriorated by heat and oxygen and easily colored, it is preferable to contain a phosphorus-based heat stabilizer as the heat stabilizer. As the phosphorus-based stabilizer, it is preferable to add a phosphite compound. Examples of the phosphite compound include a pentaerythritol-type phosphite compound, a phosphite compound that reacts with divalent phenols and has a cyclic structure, and a phosphite compound having another structure.

Specific examples of the above-mentioned pentaerythritol-type phosphite compound include distearyl pentaerythritol diphosphite, bis (2,4-di-tert-butylphenyl) pentaerythritol diphosphite, and bis (2,6). -Di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite, bis (2,6-di-tert-butyl-4-ethylphenyl) pentaerythritol diphosphite, phenylbisphenol A pentaerythritol diphosphite, Examples thereof include bis (nonylphenyl) pentaerythritol diphosphite and dicyclohexylpentaerythritol diphosphite, and among them, distearyl pentaerythritol diphosphite and bis (2,4-di-tert-butylphenyl) penta are preferable. Examples include erythritol diphosphite.

Examples of the phosphite compound having a cyclic structure by reacting with the above divalent phenols include 2,2'-methylenebis (4,6-di-tert-butylphenyl) (2,4-di-tert-butylphenyl). ) Phosphite, 2,2'-methylenebis (4,6-di-tert-butylphenyl) (2-tert-butyl-4-methylphenyl) Phosphite, 2,2'-methylenebis (4-methyl-6-) tert-butylphenyl) (2-tert-butyl-4-methylphenyl) phosphite, 2,2'-ethylidenebis (4-methyl-6-tert-butylphenyl) (2-tert-butyl-4-methylphenyl) ) Phosphite, 2,2'-methylene-bis- (4,6-di-t-butylphenyl) octylphosphite, 6-tert-butyl-4- [3-[(2,4,8,10)) -Tetra-tert-butyldibenzo [d, f] [1,3,2] dioxaphosfepine-6-yl) oxy] propyl] -2-methylphenol and the like can be mentioned.

Examples of the phosphite compound having the above other structure include triphenylphosphite, tris (nonylphenyl) phosphite, tridecylphosphite, trioctylphosphite, trioctadecylphosphite, and didecylmonophenylphosphite. , Dioctyl monophenyl phosphite, diisopropyl monophenyl phosphite, monobutyl diphenyl phosphite, monodecyldiphenyl phosphite, monooctyl diphenyl phosphite, 2,2-methylenebis (4,6-di-tert-butylphenyl) octylphos Fight, Tris (diethylphenyl) phosphite, Tris (di-iso-propylphenyl) phosphite, Tris (di-n-butylphenyl) phosphite, Tris (2,4-di-tert-butylphenyl) phosphite, And tris (2,6-di-tert-butylphenyl) phosphite and the like.

In addition to various phosphite compounds, for example, phosphate compounds, phosphonite compounds, and phosphonate compounds can be mentioned.

Phosphate compounds include tributyl phosphate, trimethyl phosphate, tricresyl phosphate, triphenyl phosphate, trichlorophenyl phosphate, triethyl phosphate, diphenyl cresyl phosphate, diphenyl monoorthoxenyl phosphate, tributoxyethyl phosphate, dibutyl phosphate, dioctyl phosphate, Examples thereof include diisopropyl phosphate, preferably triphenyl phosphate and trimethyl phosphate.

Phosphonite compounds include tetrakis (2,4-di-tert-butylphenyl) -4,4'-biphenylenediphosphonite and tetrakis (2,4-di-tert-butylphenyl) -4,3'-biphenylenedi. Phosphonite, tetrakis (2,4-di-tert-butylphenyl) -3,3'-biphenylenediphosphonite, tetrakis (2,6-di-tert-butylphenyl) -4,4'-biphenylenediphosphonite , Tetrakiss (2,6-di-tert-butylphenyl) -4,3'-biphenylenediphosphonite, tetrakis (2,6-di-tert-butylphenyl) -3,3'-biphenylenediphosphonite, bis (2,4-di-tert-butylphenyl) -4-phenyl-phenylphosphonite, bis (2,4-di-tert-butylphenyl) -3-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) Examples thereof include -3-phenyl-phenylphosphonite, tetrakis (di-tert-butylphenyl) -biphenylenediphosphonite and bis (di-tert-butylphenyl) -phenyl-phenylphosphonite are preferable, and tetrakis (2, 4-Di-tert-butylphenyl) -biphenylenediphosphonite and bis (2,4-di-tert-butylphenyl) -phenyl-phenylphosphonite are more preferred. Such a phosphonite compound is preferable because it can be used in combination with a phosphite compound having an aryl group in which the alkyl group is substituted by 2 or more.

Examples of the phosphonate compound include dimethyl benzenephosphonate, diethyl benzenephosphonate, and dipropyl benzenephosphonate.

Among the above phosphorus-based heat stabilizers, trisnonylphenyl phosphite, trimethylphosphate, tris (2,4-di-tert-butylphenyl) phosphite, bis (2,4-di-tert-butylphenyl) pentaerythritol Diphosphite, bis (2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite is preferably used.

The above phosphorus-based heat stabilizers can be used alone or in combination of two or more. The phosphorus-based heat stabilizer is preferably blended in an amount of 0.001 to 1 part by weight, more preferably 0.01 to 0.5 part by weight, and further preferably 0.01 to 0.3 part by weight per 100 parts by weight of the resin composition. Will be done.

The resin composition used in the present invention contains a hindered phenol-based heat stabilizer or a sulfur-based heat stabilizer as a heat stabilizer for the purpose of suppressing a decrease in molecular weight and deterioration of hue during extrusion / molding. It can also be added in combination with a phosphorus-based heat stabilizer.

The hindered phenol-based heat stabilizer is not particularly limited as long as it has an antioxidant function, and is, for example, n-octadecyl-3- (4'-hydroxy-3', 5'-di-t-. Butylphenyl) propionate, tetrakis {methylene-3- (3', 5'-di-t-butyl-4-hydroxyphenyl) propionate} methane, distearyl (4-hydroxy-3-methyl-5-t-butylbenzyl) ) Malonate, triethireglycol-bis {3- (3-t-butyl-5-methyl-4-hydroxyphenyl) propionate}, 1,6-hexanediol-bis {3- (3,5-di-t-) Butyl-4-hydroxyphenyl) propionate}, pentaerythrityl-tetrakis {3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate}, 2,2-thiodiethylenebis {3- (3,3) 5-di-t-butyl-4-hydroxyphenyl) propionate}, 2,2-thiobis (4-methyl-6-t-butylphenol), 1,3,5-trimethyl-2,4,6-tris (3) , 5-di-t-butyl-4-hydroxybenzyl) benzene, tris (3,5-di-t-butyl-4-hydroxybenzyl) -isocyanurate, 2,4-bis {(octylthio) methyl} -o -Cresol, Isooctyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate, 2,5,7,8-tetramethyl-2 (4', 8', 12'-trimethyltridecyl ) Chroman-6-ol, 3,3', 3 ", 5,5', 5" -hexa-t-butyl-a, a', a "-(mesitylen-2,4,6-triyl) tri- Examples thereof include p-cresol.

Among these, n-octadecyl-3- (4'-hydroxy-3', 5'-di-t-butylphenyl) propionate, pentaerythrityl-tetrakis {3- (3,5-di-t-butyl) -4-Hydroxyphenyl) propionate}, 3,3', 3 ", 5,5', 5" -hexa-t-butyl-a, a', a'-(mesitylen-2,4,6-triyl) Tri-p-cresol, 2,2-thiodiethylenebis {3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate} and the like are preferable.

One of these hindered phenolic heat stabilizers may be used alone, or two or more thereof may be used in combination.

The hindered phenolic heat stabilizer is preferably 0.001 to 1 part by weight, more preferably 0.01 to 0.5 part by weight, and further preferably 0.01 to 0.3 part by weight per 100 parts by weight of the resin composition. Partially mixed.

Examples of the sulfur-based heat stabilizer include dilauryl-3,3'-thiodipropionic acid ester, ditridecyl-3,3'-thiodipropionic acid ester, dimyristyl-3,3'-thiodipropionic acid ester, and di-dipropionic acid ester. Stearyl-3,3'-thiodipropionic acid ester, laurylstearyl-3,3'-thiodipropionic acid ester, pentaerythritol tetrakis (3-laurylthiopropionate), bis [2-methyl-4- (3) -Laurylthiopropionyloxy) -5-tert-butylphenyl] sulfide, octadecyldisulfide, mercaptobenzimidazole, 2-mercapto-6-methylbenzimidazole, 1,1'-thiobis (2-naphthol) and the like. .. Of the above, pentaerythritol tetrakis (3-laurylthiopropionate) is preferable.

One of these sulfur-based heat stabilizers may be used alone, or two or more thereof may be used in combination.

The sulfur-based heat stabilizer is preferably blended in an amount of 0.001 to 1 part by weight, more preferably 0.01 to 0.5 part by weight, and further preferably 0.01 to 0.3 part by weight per 100 parts by weight of the resin composition. Will be done.

When a phosphite-based heat stabilizer, a phenol-based heat stabilizer, and a sulfur-based heat stabilizer are used in combination, the total of these is preferably 0.001 to 1 part by weight, more preferably 0, based on 100 parts by weight of the resin composition. .01 to 0.3 parts by weight is blended.

(Release agent)
In the resin composition used in the present invention, in order to further improve the mold release property from the mold during melt molding, it is possible to add a mold release agent within a range that does not impair the object of the present invention.

Such mold release agents include higher fatty acid esters of monovalent or polyhydric alcohols, higher fatty acids, paraffin waxes, beeswax, olefin waxes, olefin waxes containing carboxy groups and / or carboxylic acid anhydride groups, silicone oils, etc. Organopolysiloxane and the like can be mentioned.

As the higher fatty acid ester, a partial ester or a total ester of a monovalent or polyvalent alcohol having 1 to 20 carbon atoms and a saturated fatty acid having 10 to 30 carbon atoms is preferable. Examples of the partial ester or total ester of the monovalent or polyvalent alcohol and the saturated fatty acid include stearic acid monoglyceride, stearic acid diglyceride, stearic acid triglyceride, stearic acid monosorbitate, stearyl stearate, behenic acid monoglyceride, and behenic acid. Behenyl, pentaerythritol monostearate, pentaerythritol tetrastearate, pentaerythritol tetrapelargonate, propylene glycol monostearate, stearyl stearate, palmityl palmitate, butyl stearate, methyl laurate, isopropyl palmitate, biphenyl biphene -To, sorbitan monostearate, 2-ethylhexyl stearate and the like.

Of these, stearic acid monoglyceride, stearic acid triglyceride, pentaerythritol tetrastearate, and behenyl behenate are preferably used.

As the higher fatty acid, a saturated fatty acid having 10 to 30 carbon atoms is preferable. Examples of such fatty acids include myristic acid, lauric acid, palmitic acid, stearic acid, behenic acid and the like.

These release agents may be used alone or in combination of two or more. The blending amount of the release agent is preferably 0.01 to 5 parts by weight with respect to 100 parts by weight of the resin composition.

(UV absorber)
The resin composition used in the present invention may contain an ultraviolet absorber. Examples of the ultraviolet absorber include benzotriazole-based ultraviolet absorbers, benzophenone-based ultraviolet absorbers, triazine-based ultraviolet absorbers, cyclic iminoester-based ultraviolet absorbers, cyanoacrylate-based ultraviolet absorbers, and the like, among which benzotriazole-based ultraviolet absorbers are used. Agents are preferred.

Examples of the benzotriazole-based ultraviolet absorber include 2- (2'-hydroxy-5'-methylphenyl) benzotriazole, 2- (2'-hydroxy-5'-tert-butylphenyl) benzotriazole, and 2- (2). '-Hydroxy-5'-tert-octylphenyl) benzotriazole, 2- (2'-hydroxy-3', 5'-di-tert-butylphenyl) benzotriazole, 2- (2'-hydroxy-3', 5'-di-tert-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" -tetraphthalimidemethyl) -5'-methylphenyl] benzotriazole , 2- (2'-Hydroxy-3'-tert-butyl-5'-methylphenyl) -5-chlorobenzotriazole, 2- (2'-hydroxy-3', 5'-di-tert-butylphenyl) -5-Chlorobenzotriazole, 2,2'methylenebis [4- (1,1,3,3-tetramethylbutyl) -6- (2H-benzotriazole-2-yl) phenol], methyl-3- [3 Examples thereof include benzotriazole-based ultraviolet absorbers typified by a condensate of −tert-butyl-5- (2H-benzotriazole-2-yl) -4-hydroxyphenylpropionate-polyethylene glycol.

The blending ratio of the ultraviolet absorber is preferably 0.03 to 2.5 parts by weight, more preferably 0.1 to 2 parts by weight, and further preferably 0.2 to 1 part by weight with respect to 100 parts by weight of the resin composition. 5 parts by weight.

(Light stabilizer)
The resin composition used in the present invention can contain a light stabilizer. When a light stabilizer is contained, it is good in terms of weather resistance and has an advantage that cracks are less likely to occur in the molded product.

Examples of the light stabilizer include 1,2,2,6,6-pentamethyl-4-piperidyl methacrylate, bis didecanoate (2,2,6,6-tetramethyl-1-octyloxy-4-piperidinyl) ester, and the like. Bis (1,2,2,6,6-pentamethyl-4-piperidinyl)-[[3,5-bis (1,1-dimethylethyl) -4-hydroxyphenyl] methyl] butylmalonate, 2,4- Bis [N-butyl-N- (1-cyclohexyloxy-2,2,6,6-tetramethylpiperidine-2-yl) amino] -6- (2-hydroxyethylamine) -1,3,5-triazine, Bis (1,2,2,6,6-pentamethyl-4-piperidinyl) sebacate, methyl (1,2,2,6,6-pentamethyl-4-piperidinyl) sebacate, bis (2,2,6,6- Tetramethyl-4-piperidyl) carbonate, bis (2,2,6,6-tetramethyl-4-piperidyl) succinate, bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, 4 -Benzoyloxy-2,2,6,6-tetramethylpiperidine, 4-octanoyloxy-2,2,6,6-tetramethylpiperidine, bis (2,2,6,6-tetramethyl-4-piperidyl) ) Diphenylmethane-p, p'-dicarbamate, bis (2,2,6,6-tetramethyl-4-piperidyl) benzene-1,3-disulfonate, bis (2,2,6,6-tetramethyl) Hindered amines such as -4-piperidyl) phenylphosphite, nickel such as nickelbis (octylphenylsulfide, nickel complex-3,5-di-t-butyl-4-hydroxybenzylphosphate monoethylate, nickeldibutyldithiocarbamate) Examples thereof include a complex. These light stabilizers may be used alone or in combination of two or more. The content of the light stabilizer is preferably 0.001 to 1 part by weight with respect to 100 parts by weight of the resin composition. More preferably, it is 0.01 to 0.5 parts by weight.

(Epoxy stabilizer)
In order to improve the hydrolyzability, the resin composition used in the present invention may contain an epoxy compound as long as the object of the present invention is not impaired.

Epoxide-based stabilizers include epoxidized soybean oil, epoxidized flaxseed oil, phenylglycidyl ether, allylglycidyl ether, t-butylphenylglycidyl ether, 3,4-epoxidecyclohexylmethyl-3', 4'-epoxidecyclohexylcarboxylate. , 3,4-Epoxide-6-methylcyclohexylmethyl-3', 4'-epoxide-6'-methylcyclohexylcarboxylate, 2,3-epoxidecyclohexylmethyl-3', 4'-epoxycyclohexylcarboxylate, 4- (3,4-Epoxide-5-methylcyclohexyl) Butyl-3', 4'-epoxycyclohexylcarboxylate, 3,4-epoxidecyclohexylethylene oxide, cyclohexylmethyl-3,4-epoxycyclohexylcarboxylate, 3,4-epoxide -6-Methylcyclohexylmethyl-6'-methylsilohexyl carboxylate, bisphenol A diglycidyl ether, tetrabromobisphenol A glycidyl ether, diglycidyl ester of phthalic acid, diglycidyl ester of hexahydrophthalic acid, bis-epoxide dicyclo Pentazienyl ether, bis-epoxyethylene glycol, bis-epoxycyclohexyl adipate, butadienediepoxide, tetraphenylethyleneepoxide, octyl epoxide, epoxidized polybutadiene, 3,4-dimethyl-1,2-epoxycyclohexane, 3, 5-Dimethyl-1,2-epoxycyclohexane, 3-methyl-5-t-butyl-1,2-epoxycyclohexane, octadecyl-2,2-dimethyl-3,4-epoxidecyclohexylcarboxylate, N-butyl-2 , 2-Dimethyl-3,4-epoxide cyclohexylcarboxylate, cyclohexyl-2-methyl-3,4-epoxycyclohexylcarboxylate, N-butyl-2-isopropyl-3,4-epoxide-5-methylcyclohexylcarboxylate, Octadecyl-3,4-epoxide cyclohexylcarboxylate, 2-ethylhexyl-3', 4'-epoxide cyclohexylcarboxylate, 4,6-dimethyl-2,3-epoxide cyclohexyl-3', 4'-epoxide cyclohexylcarboxylate, 4,5-Epoxide tetrahydrophthalic anhydride, 3-t-butyl-4,5-epoxide tetrahydrophthalic anhydride, diethyl-4,5 -Epoxy-cis-1,2-cyclohexyldicarboxylate, di-n-butyl-3-t-butyl-4,5-epoxy-cis-1,2-cyclohexyldicarboxylate and the like can be mentioned. Bisphenol A diglycidyl ether is preferable from the viewpoint of compatibility and the like.

Such an epoxy-based stabilizer is preferably 0.0001 to 5 parts by weight, more preferably 0.001 to 1 part by weight, still more preferably 0.005 to 0.5 parts by weight, based on 100 parts by weight of the resin composition. It is blended in the range of parts by weight.

(Bluing agent)
The resin composition used in the present invention may contain a bluing agent in order to counteract the yellowness of the lens based on the polymer or the ultraviolet absorber. As the bluing agent, any one used for polycarbonate can be used without any particular problem. Generally, anthraquinone dyes are easily available and preferable.

Specific examples of the brewing agent include, for example, the generic name Solvent Violet 13 [CA. No (color index No) 60725], generic name Solvent Violet31 [CA. No 68210, generic name Solvent Violet33 [CA
.. No 60725], generic name Solvent Blue94 [CA. No 61500], generic name Solvent Violet36 [CA. No 68210], generic name Solvent Blue97 [Bayer's "Macrolex Violet RR"] and generic name Solvent Blue45 [CA. No61110] is a typical example.

These brewing agents may be used alone or in combination of two or more. These bluing agents are preferably blended in a ratio of ^{0.1 × 10 -4} to 2 × 10 ^-4 parts by weight with respect to 100 parts by weight of the resin composition.

(Flame retardants)
A flame retardant can also be added to the resin composition used in the present invention. Flame retardants include halogen-based flame retardants such as brominated epoxy resin, brominated polystyrene, brominated polycarbonate, brominated polyacrylate, and chlorinated polyethylene, and phosphate ester-based flame retardants such as monophosphate compounds and phosphate oligomeric compounds. Organic phosphorus flame retardants other than phosphoric acid ester flame retardants such as phosphinate compounds, phosphonate compounds, phosphonitrile oligomer compounds, and phosphonic acid amide compounds, organic sulfonic acid alkali (earth) metal salts, borate metal salt flame retardants, Includes organic metal salt flame retardants such as metal tinic acid flame retardants, silicone flame retardants, ammonium polyphosphate flame retardants, triazine flame retardants and the like. Separately, a flame retardant aid (for example, sodium antimonyate, antimony trioxide, etc.), a drip inhibitor (polytetrafluoroethylene having a fibril-forming ability, etc.) and the like may be blended in combination with the flame retardant.

Among the above-mentioned flame retardants, compounds that do not contain chlorine atoms and bromine atoms are one of the features that reduce the environmental load because they reduce the factors that are considered unfavorable when incinerating waste or thermal recycling. It is more suitable as a flame retardant in the molded product of the present invention.

When the flame retardant is blended, the range is preferably 0.05 to 50 parts by weight per 100 parts by weight of the resin composition. Sufficient flame retardancy is exhibited at 0.05 parts by weight or more, and the strength and heat resistance of the molded product are excellent at 50 parts by weight or less.

(Elastic polymer)
In the resin composition used in the present invention, an elastic polymer can be used as an impact improver, and examples of the elastic polymer include natural rubber or a rubber component having a glass transition temperature of 10 ° C. or less. Examples thereof include graft copolymers in which one or more of monomers selected from aromatic vinyl, vinyl cyanide, acrylic acid ester, methacrylic acid ester, and vinyl compounds copolymerizable with these are copolymerized. can. A more suitable elastic polymer is a core-shell type graft copolymer in which one or more shells of the above-mentioned monomers are graft-copolymerized on the core of the rubber component.

In addition, a block copolymer of such a rubber component and the above-mentioned monomer can also be mentioned. Specific examples of such block copolymers include thermoplastic elastomers such as styrene / ethylenepropylene / styrene elastomer (hydrogenated styrene / isoprene / styrene elastomer) and hydrogenated styrene / butadiene / styrene elastomer. Furthermore, various elastic polymers known as other thermoplastic elastomers, such as polyurethane elastomers, polyester elastomers, and polyetheramide elastomers, can also be used.

A more suitable impact improver is a core-shell type graft copolymer. In a core-shell type graft copolymer, the particle size of the core is 0.05 in terms of weight average particle size.
~ 0.8 μm is preferable, 0.1 to 0.6 μm is more preferable, and 0.1 to 0.5 μm is even more preferable. Better bending resistance is achieved in the range of 0.05 to 0.8 μm. The elastic polymer preferably contains 40% or more of a rubber component, and more preferably 60% or more.

Rubber components include butadiene rubber, butadiene-acrylic composite rubber, acrylic rubber, acrylic-silicone composite rubber, isobutylene-silicone composite rubber, isoprene rubber, styrene-butadiene rubber, chloroprene rubber, ethylene-propylene rubber, nitrile rubber, ethylene- Acrylic rubber, silicone rubber, epichlorohydrin rubber, fluororubber, and those in which hydrogen is added to these unsaturated bond portions can be mentioned, but they contain halogen atoms from the viewpoint of concern about the generation of harmful substances during combustion. A non-rubber component is preferable in terms of environmental load.

The glass transition temperature of the rubber component is preferably −10 ° C. or lower, more preferably −30 ° C. or lower, and the rubber component is particularly preferably butadiene rubber, butadiene-acrylic composite rubber, acrylic rubber, or acrylic-silicone composite rubber. The composite rubber refers to a rubber obtained by copolymerizing two kinds of rubber components or a rubber polymerized so as to have an IPN structure in which they are intertwined with each other so as not to be separated.

Examples of aromatic vinyl in the vinyl compound copolymerized with the rubber component include styrene, α-methylstyrene, p-methylstyrene, alkoxystyrene, halogenated styrene, and the like, and styrene is particularly preferable. Examples of the acrylic acid ester include methyl acrylate, ethyl acrylate, butyl acrylate, cyclohexyl acrylate, and octyl acrylate, and examples of the methacrylic acid ester include methyl methacrylate, ethyl methacrylate, and methacrylic acid. Butyl, cyclohexyl methacrylate, octyl methacrylate and the like can be mentioned, and methyl methacrylate is particularly preferable. Among these, it is particularly preferable to contain a methacrylic acid ester such as methyl methacrylate as an essential component. More specifically, the methacrylic acid ester is contained in 100% by weight of the graft component (in 100% by weight of the shell in the case of a core-shell type polymer), preferably 10% by weight or more, and more preferably 15% by weight or more. Will be done.

The elastic polymer containing a rubber component having a glass transition temperature of 10 ° C. or lower may be produced by any of bulk polymerization, solution polymerization, suspension polymerization, and emulsion polymerization, and the copolymerization method is as follows. It does not matter whether it is a one-stage graft or a multi-stage graft. Further, it may be a mixture with a copolymer containing only a graft component produced as a by-product during production. Further, as the polymerization method, in addition to the general emulsion polymerization method, a soap-free polymerization method using an initiator such as potassium persulfate, a seed polymerization method, a two-step swelling polymerization method and the like can be mentioned. Further, in the suspension polymerization method, a method in which the aqueous phase and the monomer phase are individually held and both are accurately supplied to a continuous disperser, and the particle size is controlled by the rotation speed of the disperser, and continuous production. In the method, a method of controlling the particle size by supplying the monomer phase into an aqueous liquid having dispersibility by passing it through a small-diameter orifice or a porous filter having a diameter of several to several tens of μm may be used. In the case of a core-shell type graft polymer, the reaction may be one-stage or multi-stage for both the core and the shell.

Such elastic polymers are commercially available and easily available. For example, as the rubber component, butadiene rubber, acrylic rubber or butadiene-acrylic composite rubber is mainly used as Kaneace B series (for example, B-56) of Kanebuchi Chemical Industry Co., Ltd. and Metabren of Mitsubishi Rayon Co., Ltd. C series (eg C-223A etc.), W series (eg W-450A etc.), Kureha Chemical Industry Co., Ltd. Pararoid EXL series (eg EXL-2602 etc.), HIA series (eg HIA-15 etc.), BTA series (For example, BTA-III, etc.), KCA series, Rohm & Hearth's Pararoid EXL series, KM series (for example, KM-336P, KM-357P, etc.), and Ube Psycon Co., Ltd.'s UCL modifier resin series (UMG).・ UMG AXS resin series of ABS Co., Ltd.), etc., and those containing acrylic-silicone composite rubber as the rubber component are commercially available from Mitsubishi Rayon Co., Ltd. under the trade name of Metabren S-2001 or SRK-200. Some are listed.

The composition ratio of the impact improver is preferably 0.2 to 50 parts by weight, preferably 1 to 30 parts by weight, and more preferably 1.5 to 20 parts by weight per 100 parts by weight of the resin composition. Such a composition range can impart good bending resistance to the composition while suppressing a decrease in rigidity.

(Carbodiimide)
The resin composition used in the present invention preferably contains carbodiimide in order to suppress deterioration of hue in a moist heat environment. The carbodiimide is not particularly limited as long as it is a compound having an "-N = C = N-" structure in the molecule. Examples of the carbodiimide compound include a monocarbodiimide compound, a polycarbodiimide compound, a cyclic carbodiimide compound, and the like, which are generally widely known, and any of them can be used. Examples of the carbodiimide compound include JP-A-9-309871, JP-A-9-249801, JP-A-9-208649, JP-A-9-296097, JP-A-8-81,533, JP-A-8-27092, and JP-A-9-136869. JP-A-9-124582, JP-A-9-188807, JP-A-2005-82642, JP-A-2005-53870, JP-A-2012-36392, JP-A-2010-163203, JP-A-2011-174094, WO2008 / 072514, WO2010 / 071211, Examples thereof include those described in JP-A-2012-81759, JP-A-2012-52014, JP-A-2012-7079 and the like.

The molecular weight of carbodiimide is preferably 150 or more, more preferably 185 or more, still more preferably 200 or more. Within such a range, good storage stability can be obtained in addition to improvement of moisture resistance. The molecular weight of carbodiimide is preferably 13000 or less, more preferably 8000 or less, and further preferably 4000 or less. Within such a range, the compatibility with the polycarbonate resin and the acrylic resin is excellent, and the transparency of the molded product is excellent, which is preferable.

In the present specification, when carbodiimide is a polymer, the molecular weight of carbodiimide means "mass average molecular weight". Here, the mass average molecular weight of carbodiimide is a polystyrene-equivalent mass average molecular weight measured by a gel permeation chromatography (GPC) method. Specifically, the polystyrene-equivalent mass average molecular weight of carbodiimide is used as a measuring device. Using LC-9A / RID-6A manufactured by Shimadzu Corporation as a column, Shodex K-800P / K-804L / K-804L manufactured by Showa Denko Corporation as a column, and chloroform or the like as a mobile phase, the column temperature is 40 ° C. It can be measured using a standard polystyrene calibration curve.

As the carbodiimide, any of monocarbodiimide, polycarbodiimide and cyclic carbodiimide can be used, but cyclic carbodiimide and polycarbodiimide are more preferable.

As the polycarbodiimide, a commercially available product may be used, for example, an aliphatic polycarbodiimide (“HMV-8CA”, “LA-1” manufactured by Nisshinbo Chemical Co., Ltd.) and a carbodiimide-modified isocyanate (“Carbodilite V-05” manufactured by Nisshinbo Chemical Co., Ltd.). ") And so on. Of these, aliphatic polycarbodiimides ("HMV-8CA" and "LA-1" manufactured by Nisshinbo Chemical Co., Ltd.) are preferable.

(Manufacturing method of sheet or film)
In the method for producing a sheet or film of the present invention, the molten resin composition melt-extruded from the die is cooled by sequentially externally contacting three cooling rolls in the order of a first cooling roll, a second cooling roll, and a third cooling roll. It is preferably produced by a melt film forming method that is taken over later. The extruder used for the melt extrusion includes a hopper section for supplying the resin composition, a cylinder section for melting the resin composition, a screw for biting the resin composition into the cylinder and moving the molten resin composition, and a molten resin composition. It is preferable to have a gear pump for moving an object by a certain amount, a filter for removing foreign substances in the molten resin composition, and a die for extruding the molten resin composition. Prior to melt extrusion, it is preferable that the resin composition is sufficiently dried to remove moisture and air inside. Preliminary drying treatment is preferable because it can prevent foaming of the obtained sheet or film and thermal deterioration of the resin composition.

The water content of the pellets preferably used in the method for producing a sheet or film of the present invention is preferably 1,000 ppm or less, more preferably 500 ppm or less. It is preferable to dry the pellets using a dryer having a dehumidifying function because it has the effect of shortening the drying time. The drying temperature of the pellets is preferably set lower than the glass transition temperature of the resin composition, preferably (Tg-20) to (Tg-15) ° C, more preferably (Tg-15) to (Tg-5) ° C. Is. When the drying temperature is set to Tg ° C. or higher, the pellets may be semi-melted and the pellets may stick to each other. Further, if the drying temperature is low, the drying becomes insufficient.

In an extruder used for melt extrusion, a method of replacing the atmosphere in the hopper with hot nitrogen gas or circulating hot nitrogen gas in order to prevent the acceleration of thermal deterioration of the resin composition due to air (oxygen) in the hopper. It is also preferably adopted to make the hopper and hopper in an oxygen-free state by putting it in a vacuum state. The nitrogen flow rate is preferably 2 to 6 l / min. More preferably, it is 3 to 5 l / min, and the pressure inside the hopper is preferably positive. If it is less than the lower limit, the hopper may not be sufficiently positive pressure. In addition, if the upper limit is exceeded, the amount of outflow to the outside of the hopper increases, and there is a concern that the oxygen concentration may decrease due to external leakage. In the case of creating a vacuum state, it is preferable that the degree of vacuum is -100 kPa or less when the screw barrel portion is filled with resin. If the degree of vacuum is insufficient, there may be gaps in the flange including the hopper and other joints, and the oxygen-free state may not be obtained.

The resin composition charged into the hopper is then bitten into the extruder by the screw biting portion (supplying section) at the supply port. At this time, the resin becomes sticky between the biting start portion and the barrel portion of the screw and becomes entangled with the screw, which hinders the subsequent supply of the resin composition, and the resin composition stays at the same point in the extruder for a long time. Due to the retention, brown or black heat-deteriorated substances may be gradually generated, or the discharge amount may fluctuate. In order to avoid such a problem, it is preferable to water-cool the barrel portion in the vicinity of the screw biting portion. Then, by the movement of the screw of the extruder, it moves in the extruder direction in the die direction. At this time, for example, a heat-deteriorated product of the resin composition is generated as much as possible in the flange portion connecting the tip of the extruder and the gear pump, the conduit of the molten resin composition, the conduit connecting the filter housing and the extrusion die, the filter housing portion, and the like. It is preferable not to do so. Therefore, for example, it is preferable to prevent the resin composition from staying locally by forming a structure so that the conduit does not bend suddenly.

Further, it is preferable that the extruder has a structure that does not have a vent function for vacuum degassing after the resin composition is melted, from the viewpoint of not providing a retention portion. The discharge capacity of the extruder is set in consideration of the above-mentioned preferable residence time. From an industrial point of view, for example, when producing a film having a width of about 1,000 mm and a thickness of about 50 μm, it is preferable to select an extruder having a maximum discharge rate of about 130 kg / h. By using such an extruder, a film having a width of 1,100 mm and a thickness of 50 μm can be formed at a speed of about 30 m / min using a die having a width of 1,200 mm. As the screw, a screw usually used for melt-extruding the resin composition can be used, and a single-screw screw is preferable. Further, as the screw shape, a full flight structure or a double flight structure can be applied, and it is preferable that the screw shape has a sufficient groove depth for efficiently discharging the gas generated in the extruder cylinder toward the hopper. The groove depth in the pellet supply portion of the screw is preferably 5 to 10 mm, more preferably 6 to 8 mm. If the groove depth is deeper than 10 mm, pellet biting becomes excessive, and an increase in screw torque may cause screw breakage. Further, when the groove depth is shallower than 5 mm, the pellet biting becomes unstable and the discharge amount may not be stable. At this time, it is preferable that the set temperatures of the extruder cylinder and the piping are set so that the difference from the temperature of the discharged resin composition is within + 15 ° C. More preferably, it is within + 10 ° C. When a temperature difference of more than + 15 ° C. occurs, it indicates that the resin composition is abnormally generating heat due to screw shearing, which promotes low molecular weight and gelation of the resin due to shearing. .. Further, it is preferable that the screw has a structure in which shearing is not easily applied, and the compression ratio of the screw is preferably less than 2.50. The compression ratio of the screw is more preferably 1.30 or more and less than 2.50, and further preferably 1.50 or more and 2.30 or less. If the compression ratio of the screw is less than 1.30, the kneading of the resin composition becomes insufficient and the molten state becomes unstable. Since the kneading part and the measuring part at the screw tip do not affect the compression ratio, the shape can be freely selected. However, a structure in which unmelted pellets such as Maddock are forcibly melted is not preferable because it promotes heat generation. Further, it is preferable to promote dispersion in the screw kneading portion, and it is more preferable to have a kneading structure that promotes elongation deformation such as elongation deformation type wave and CRD mixing.

The filter preferably has a structure including a leaf disk-shaped or pleated-shaped filter element having a required filtration area and a cylindrical housing for holding the filter element. As the filter element, a known one can be used, but it is preferable to use a commercially available metal heat-resistant and pressure-resistant filter element such as a sintered metal type or an aggregate type of ultrafine metal fibers.

The melt extrusion die used in the present invention is a T-die (coat hanger type die) in which the resin composition is supplied from the central portion in the width direction of the die, or a T-die divided into two by the inflow portion of the resin composition. It is preferable to use a known type I-die or the like in which the resin composition flows in from one end in the width direction of the die. It is preferable that the lip, which is the portion of the extrusion die where the resin composition is discharged, is finished in a sufficiently smooth shape. In the present invention, the lip opening (opening of the die) is preferably in the range of 5t to 25t, more preferably in the range of 7t to 20t, where t is the desired film thickness. Specifically, for example, in the case of a film having a thickness of 100 μm, the lip opening degree is preferably 0.5 to 2.5 mm, more preferably 0.7 mm to 2.0 mm. By adjusting the lip opening degree within such a range, the shear stress applied to the discharged resin composition by the die lip is reduced, and the birefringence, particularly the in-plane birefringence, can be suppressed to a small value. Further, since the lip opening is sufficiently wide with respect to the film thickness, there is also an advantageous effect that the die streaks caused by contact with scratches and deposits of the die lip are reduced. When used for optical applications, it is desirable to suppress the die streaks of the film as much as possible. For automatic adjustment of thickness unevenness, the lip bolt of the die is mechanically rotated to adjust the lip opening, or a heating device is attached to the die lip at regular intervals, and the temperature is adjusted individually to adjust the viscosity of the molten resin. It is preferable to adopt a method (temperature lip) in which the film thickness is adjusted by utilizing the temperature change.

The ratio R2 / R1 of the peripheral speed R2 of the second cooling roll to the peripheral speed R1 of the first cooling roll is preferably 1.050 to 1.100, more preferably 1.050 to 1.080. The drawdown phenomenon, which is a problem during thermoforming, can be suppressed by increasing the heat shrinkage of the film. The heat shrinkage of the film can be adjusted by the stretching ratio when the unstretched film is stretched, but the cooling roll temperature during film formation of the unstretched film is controlled within an appropriate range, and a speed difference is added between the cooling rolls to make a slight difference. It can also be adjusted by stretching. The method of giving a speed difference between the cooling rolls is preferably used because it does not require a longitudinal stretching facility and is a simple method. If the ratio R2 / R1 is too small, the heat shrinkage rate of the film becomes too small, which induces drawdown during heat molding. If the ratio R2 / R1 is too large, the heat shrinkage rate of the film becomes too large, shrinkage stress remains in the thermoformed product, and strain may occur, which is not preferable. In order to precisely control the speed ratio of the cooling rolls, it is preferable that each cooling roll is a facility capable of controlling the peripheral speed with an accuracy of 0.01%.

The temperature of the first cooling roll used in the method for producing a sheet or film of the present invention is preferably (Tg-7) to (Tg) ° C., where the glass transition temperature of the resin composition is (Tg) ° C. , (Tg-5) to (Tg) ° C. is more preferable, and more preferably (Tg-3) ° C. to (Tg-1) ° C. When the temperature of the first cooling roll is lowered beyond the above range, the adhesion of the sheet or film to the roll is lowered, and as a result, air is easily entrained, and a slight slip occurs between the roll and the sheet or film. .. Therefore, a phenomenon occurs in which the sheet or film is excessively cooled and the film thickness cannot be made uniform, which is not preferable. On the other hand, if the temperature of the cooling roll is higher than the above range, the adhesiveness of the sheet or film to the roll becomes too high, and when the sheet or film is peeled off from the roll, the sheet or film is scratched or distorted. It becomes easy and is not preferable. The temperature of the second cooling roll is preferably in the range of (Tg-25) ° C. to (Tg-15) ° C. When the temperature of the second cooling roll is lowered beyond the above range, the adhesion of the sheet or film to the roll is lowered, and as a result, air is easily entrained, and a slight slip occurs between the roll and the sheet or film. .. Therefore, scratches may occur on the surface of the cooled sheet or film.

Further, the temperature of the third roll is preferably set to be 5 to 10 ° C. lower than the temperature of the second cooling roll. It is preferable to use one in which the surface temperature of the first to third cooling rolls can be controlled uniformly. In order to keep the surface temperature of the roll uniform, it is preferable to flow a cooling medium having a controlled temperature inside. Further, it is preferable to use a cooling roll surface having a mirror surface, and a material made of a material such as hard chrome or ceramic is preferably used.

In the method of the present invention, the film forming speed of the sheet or film is not particularly limited, and can be appropriately set within a range that satisfies the physical characteristics of the sheet or film. From the viewpoint of productivity, it is desirable that the film forming speed is high, but if it is too fast, the adhesion to the roll may be lowered due to the entrainment of air in the cast portion, and the homogeneity of the sheet or film may be impaired. The preferred film forming speed is 2 to 50 m / min, more preferably 5 to 30 m / min, as the peripheral speed R1 of the first cooling roll.

In the sheet or film of the present invention, the thickness thereof is preferably 30 μm or more, more preferably 50 μm or more, further preferably 75 μm or more, and the thickness is preferably 500 μm or less, more preferably 300 μm or less, further preferably 200 μm or less, and further preferably 180 μm. The following is particularly preferable, and 170 μm or less is most preferable. When the thickness of the sheet or film is within the above range, it can have excellent surface hardness and heat resistance, as well as excellent acid resistance and chemical resistance.

Further, in order to have better acid resistance and chemical resistance, the thickness of the sheet or film of the present invention is preferably 90 μm or more, more preferably 100 μm or more, further preferably 120 μm or more, particularly preferably 140 μm or more. Most preferably 150 μm or more.

Further, the sheet or film of the present invention has excellent transparency, and its haze is preferably 2.5% or less, more preferably 1.0% or less, and further preferably 0.5% or less. preferable.

(surface treatment)
The sheet or film of the present invention can be subjected to various surface treatments. Surface treatment here means a new layer on the surface layer of resin molded products such as vapor deposition (physical vapor deposition, chemical vapor deposition, etc.), plating (electroplating, electroless plating, hot-dip plating, etc.), painting, coating, printing, etc. It is to be formed, and a commonly used method can be applied. Specific examples of the surface treatment include various surface treatments such as hard coat, water / oil repellent coat, ultraviolet absorption coat, infrared absorption coat, and metallizing (evaporation, etc.). Hard coat is a particularly preferred and required surface treatment.

(Aspect 2 of the present invention)
The present invention is a laminate formed from a sheet layer formed of a thermoplastic resin (D) and (II) a film layer formed on at least one side of the sheet layer, wherein the film layer has a repeating unit as a repeating unit. It consists of a unit (a) represented by the following formula (1), a unit (b) represented by the following formula (2), and a carbonate unit (c) other than the unit (a) and the unit (b). Among the repeating units, the polycarbonate resin (A) containing 5 to 85 mol% of the unit (a), 15 to 95 mol% of the unit (b), and 0 to 80 mol% of the unit (c), and the repeating unit have the following formula ( It consists of a unit (a) represented by 1), a unit (b) represented by the following formula (2), and a carbonate unit (c) other than the unit (a) and the unit (b). , A film formed from a resin composition containing a polycarbonate resin (B) containing less than 5 mol% of the unit (a), 30 to 100 mol% of the unit (b), and 0 to 70 mol% of the unit (c). It is a laminated body that is a layer.

(In the formula, W represents an alkylene group having 1 to 20 carbon atoms or a cycloalkylene group having 6 to 20 carbon atoms, and R has a branched or linear alkyl group having 1 to 20 carbon atoms or a substituent. It represents a cycloalkyl group having 6 to 20 carbon atoms, and m represents an integer of 0 to 10.)

(Sheet layer formed from thermoplastic resin (D))
The laminate of the present invention contains a sheet layer formed of a thermoplastic resin (D). The thermoplastic resin sheet layer is not particularly limited, and various resin sheets can be used.

The thermoplastic resin (D) may contain either an amorphous resin or a crystalline resin as a main component, but among the non-crystalline thermoplastic resins, the cost and adhesion, and the handling property of the obtained laminated thermoplastic resin film From the above viewpoints, a polycarbonate resin, a polyester resin, and an acrylic resin are preferable, a polycarbonate resin and an acrylic resin are more preferable, and a polycarbonate resin is particularly preferable.

The polycarbonate-based resin is preferably an aromatic polycarbonate resin, and may be either a homopolymer or a copolymer. Further, the aromatic polycarbonate resin may have a branched structure, a linear structure, or a mixture of the branched structure and the linear structure. As the method for producing the aromatic polycarbonate resin used in the present invention, any known method such as a phosgene method, a transesterification method and a pyridine method may be used. Typical examples of the divalent phenol used for producing polycarbonate include bisphenols, and 2,2-bis (4-hydroxyphenyl) propane, that is, bisphenol A is particularly preferably used. Further, a part or all of bisphenol A may be replaced with another divalent phenol. The thermoplastic resin (D) may be used alone or in combination of two or more.

Examples of the acrylic resin include the following compounds as monomers used in the acrylic resin. For example, methyl methacrylate, methacrylic acid, acrylic acid, benzyl (meth) acrylate, n-butyl (meth) acrylate, i-butyl (meth) acrylate, t-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, Lauryl (meth) acrylate, tridecyl (meth) acrylate, stearyl (meth) acrylate, glycidyl (meth) acrylate, hydroxypropyl (meth) acrylate, 2-methoxyethyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, cyclohexyl (Meta) acrylate, isobornyl (meth) acrylate, norbornyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, tetrahydrofurfuryl (meth) Acrylate, acrylic (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2- (meth) acroyloxyethyl succinate, 2- (meth) acroyloxyethyl maleate, 2- (meth) acroyl phthalate Oxyethyl, 2- (meth) acrylic oil oxyethyl, pentamethylpiperidyl (meth) acrylate, tetramethylpiperidyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, cyclopentyl methacrylate , Cyclopentyl acrylate, cyclohexyl methacrylate, cyclohexyl acrylate, cycloheptyl methacrylate, cycloheptyl acrylate, cyclooctyl methacrylate, cyclooctyl acrylate, cyclododecyl methacrylate, cyclododecyl acrylate and the like. These may be polymerized alone or may be used by polymerizing two or more kinds.

In particular, it is preferable to contain methyl methacrylate and methyl acrylate. As the monomer component, it is preferable to contain 50 to 99 mol% of methyl methacrylate and 1 to 50 mol% of methyl acrylate, and more preferably 60 to 99 mol% of methyl methacrylate and 1 to 40 mol% of methyl acrylate. It is even more preferable to contain 70 to 99 mol% of methyl acrylate and 1 to 30 mol% of methyl acrylate. When methyl methacrylate is more than 99 mol% as the monomer component, the heat-decomposability is inferior, and molding defects such as silver may occur during molding. When methyl methacrylate is less than 50 mol% as the monomer component, the thermal deformation temperature may decrease.

The thermoplastic resin used in the present invention is a heat stabilizer, a plasticizer, a light stabilizer, a polymer metal inactivating agent, a flame retardant, a lubricant, an antistatic agent, a surfactant, and an antibacterial agent, depending on the application and need. , UV absorbers, mold release agents, colorants, impact modifiers and other additives can be added.

(Film layer formed on at least one side of the sheet layer)
The laminate of the present invention contains a specific polycarbonate resin (A) and a specific polycarbonate resin (B) as a film layer formed on at least one surface of the sheet layer, and if desired, further an acrylic resin (C). ) Is a film layer formed from a resin composition containing.

(Polycarbonate resin (A))
As the polycarbonate resin (A) used in the resin composition of the present invention, the same polycarbonate resin (A) as described in the above-mentioned (Aspect 1 of the present invention) is used.

(Polycarbonate resin (B))
As the polycarbonate resin (B) used in the resin composition of the present invention, the same polycarbonate resin (B) as described in the above-mentioned (aspect 1 of the present invention) is used.

(Manufacturing method of polycarbonate resin)
The method for producing the polycarbonate resin (A) and the polycarbonate resin (B) used in the present invention is the same as the method for producing the polycarbonate resin described in the above-mentioned (Aspect 1 of the present invention).

(Specific viscosity: η _SP )
The specific viscosity of the polycarbonate resin (A) and the polycarbonate resin _(B) (η _SP), is similar to that described above specific viscosity described in (aspect 1 of the present invention) (eta _SP).

(Acrylic resin (C))
As the acrylic resin (C) preferably used in the present invention, the same acrylic resin (C) as described in the above-mentioned (Aspect 1 of the present invention) is used.

(Manufacturing method of resin composition containing polycarbonate resin and acrylic resin)
The method for producing the resin composition used in the present invention is the same as the method for producing the resin composition described in the above-mentioned (Aspect 1 of the present invention).

(Weight ratio)
The weight ratio of the polycarbonate resin (A) to the polycarbonate resin (B) is the same as the weight ratio described in the above-mentioned (Aspect 1 of the present invention).
The weight ratio of the mixture of the polycarbonate resin (A) and the polycarbonate resin (B) to the acrylic resin (C) is the same as the weight ratio described in the above-mentioned (Aspect 1 of the present invention).

(Glass transition temperature: Tg)
The glass transition temperature (Tg) of the resin composition used in the present invention is the same as the glass transition temperature (Tg) described in the above-mentioned (Aspect 1 of the present invention).

(Pencil hardness)
The pencil hardness of the resin composition used in the present invention is the same as the pencil hardness described in the above-mentioned (Aspect 1 of the present invention).

(Additive)
As the various additives used in the present invention, the same additives as those described in the above-mentioned (Aspect 1 of the present invention) are used.

(Manufacturing method of laminated body)
As a method for producing the laminate of the present invention, known methods such as coextrusion, extrusion lamination, thermal lamination, and dry lamination can be used. Of these, it is particularly preferable to use the coextrusion method.

In the case of coextrusion, the resins constituting each layer of the laminate and the additives are merged through a feed block or a multi-manifold die using a plurality of extruders to form the laminate. In order to further improve the strength and impact resistance of the laminate, the laminate obtained in the above step can be stretched uniaxially or biaxially by a roll method, a tenter method, a tubular method or the like.

The laminate of the present invention is excellent in transparency, acid resistance, chemical resistance, surface hardness, flexibility and adhesion. Therefore, the use of the laminate of the present invention is not particularly limited, but for example, transparent sheets for building materials, interior parts, display covers, resin-coated metal plate sheets, molding (vacuum / pressure molding, hot press molding). It can be used for sheets, colored plates, transparent plates, shrink films, shrink labels, shrink tubes, automobile interior materials, resin glazing, home appliance parts, OA equipment parts, etc.

(Thickness of laminate)
In the laminated body of the present invention, the thickness of the sheet layer is preferably 100 μm or more and 500 μm or less, more preferably 120 μm or more and 400 μm or less, and further preferably 150 μm or more and 300 μm or less.

The thickness of the film layer is preferably 25 μm or more and 250 μm or less, more preferably 30 μm or more and 250 μm or less, further preferably 35 μm or more and 200 μm or less, and particularly preferably 40 μm or more and 180 μm or less.

Further, the ratio of the film layer to the total thickness of the laminated body is preferably 3% or more and 30% or less, more preferably 5% or more and 25% or less, and 10% or more and 20% or less. Is even more preferable. As long as the thickness of the film layer is within such a range, it is possible to provide a laminate having excellent surface hardness and heat resistance, and also having excellent flexibility.

Further, the laminate of the present invention is excellent in transparency, and its haze is preferably 2.5% or less, more preferably 1.0% or less, and further preferably 0.5% or less. ..

(surface treatment)
The laminate of the present invention can be subjected to various surface treatments described in the above-mentioned (Aspect 1 of the present invention).

Hereinafter, the present invention will be described in detail with reference to Examples, but the present invention is not limited thereto. In the examples, "part" means "part by weight". The resin used and the evaluation method used in the examples are as follows.

1. 1. Polymer composition ratio (NMR)
Each repeating unit was measured by proton NMR of JNM-AL400 manufactured by JEOL Ltd., and the polymer composition ratio (molar ratio) was calculated.

2. It was determined using an Ostwald viscometer from a solution prepared by dissolving 0.7 g of a polycarbonate resin in 100 ml of methylene chloride at a specific viscosity of 20 ° C.
Specific viscosity (η _SP ) = (t-t ₀ ) / t ₀
[T ₀ is the number of seconds for methylene chloride to fall, t is the number of seconds for the sample solution to fall]

3. 3. Surface hardness Based on JIS K5400, a pencil was placed at 45 degrees to the surface of the first layer (the film layer side made of the resin composition) of the film and laminate sample cut out to 80 mm × 60 mm in a thermostatic chamber with an atmospheric temperature of 23 ° C. A line was drawn with a load of 750 g applied while maintaining the angle of, and the surface condition was visually evaluated.

4. The haze film and the sheet sample that were melt-pressed together were cut into a size of 50 × 50 mm, and measured using a haze meter SH-7000 manufactured by Nippon Denshoku Kogyo Co., Ltd. under the conditions of a D65 light source and 10 °.
⊚: 0.5% or less ○: 0.5% or more and 1.0% or less Δ: 1.0% or more and 2.5% or less ×: 2.5% or more

5. Chemical resistance A film and a sheet sample that has been melt-pressed are cut into 50 x 50 mm pieces, and a commercially available tanning cream (Nutrosina) is uniformly applied to the film and sheet (film layer side) sample surface at 80 ° C. 4 After time heat treatment, the surface is washed with a neutral detergent, and the appearance of the film surface after wiping with a cloth is measured with a D65 light source and 10 ° conditions using a haze meter SH-7000 manufactured by Nippon Denshoku Kogyo Co., Ltd. And evaluated.
〇; Haze change amount 35% or less Δ; Haze change amount more than 35% and 45% or less ×; Haze change amount more than 45%

6. An acid-resistant film and a sheet sample that was melt-pressed together were cut into 100 × 150 mm, heat-treated at 85 ° C. for 1 hour, and then a commercially available phosphoric acid aqueous solution was diluted to 30% by weight, and 1 ml was added to the film and sheet (1 ml). It was dropped on the surface (on the film layer side), dried at 85 ° C. for 30 minutes, and then wiped off with a cloth, and the appearance of the film surface was observed.
〇; As a result of observing at n = 3, there was no tear or hole Δ; As a result of observing at n = 3, one or two were torn and there was a hole ×; , All torn and perforated

7. The flexible film and the sheet sample that was melt-pressed were cut into 50 × 50 mm, bent at 180 ° C so that both ends were folded together, and the change in the bent portion was observed.
〇; does not break ×; breaks

8. Adhesion A sheet sample that has been melt-pressed is cut into 50 x 50 mm pieces, and 100 squares of scratches are made from the sheet (film layer side) surface to the interface layer with a width of 1 mm using the cross-cut method, and tape is applied to the squares. Was pasted and peeled off.
〇; No peeling of all 100 squares ×; Peeling of 1 or more squares occurred

[Polycarbonate resin (A)]
ISS-PC1 (Example):
Structural unit derived from isosorbide (hereinafter ISS) / 3,9-bis (2-hydroxy-1,1-dimethylethyl) -2,4,8,10-tetraoxaspiro (5,5) undecane (hereinafter SPG) Structural unit derived from / 1,9-nonanediol (hereinafter referred to as ND) = 73/21/6 (mol%), specific viscosity 0.378
[Polycarbonate resin (B)]
ISS-PC2 (Example)
Structural unit derived from ISS / structural unit derived from ND = 88/12 (mol%), specific viscosity 0.366
[Acrylic resin (C)]
Daicel Evonik ACRYPET 8N

(Manufacturing of Polycarbonate Resin (A))
Isosorbide (hereinafter abbreviated as ISS) 369 parts, 3,9-bis (2-hydroxy-1,1-dimethylethyl) -2,4,8,10-tetraoxaspiro (5,5) undecane (hereinafter abbreviated as SPG) ) 221 parts, 1,9-nonanediol (hereinafter abbreviated as ND) 33 parts, diphenyl carbonate (hereinafter abbreviated as DPC) 750 parts, and tetramethylammonium hydroxide 0.8 × ^10-2 parts as a catalyst and barium stearate. 0.6 × 10 ^-4 parts were heated to 200 ° C. in a nitrogen atmosphere to melt them. Then, the temperature was raised to 220 ° C. and the degree of decompression was adjusted to 20.0 kPa over 30 minutes. Then, the temperature was raised to 240 ° C. and the degree of decompression was adjusted to 10 kPa over another 30 minutes. After holding at that temperature for 10 minutes, the degree of decompression was set to 133 Pa or less over 1 hour. After completion of the reaction, the mixture was discharged from the bottom of the reaction tank under nitrogen pressurization, cooled in a water tank, and cut with a pelletizer to obtain pellets (ISS-PC1).

(Manufacturing of Polycarbonate Resin (B))
445 parts of isosorbide (hereinafter abbreviated as ISS), 67 parts of 1,9-nonanediol (hereinafter abbreviated as ND), 750 parts of diphenyl carbonate (hereinafter abbreviated as DPC), and 0.0025 parts of barium stearate as a catalyst under a nitrogen atmosphere. It was heated to 120 ° C. and melted. Then, the liquid was sent to the reaction vessel, the heat medium temperature of the capacitor was adjusted to 40 ° C., the resin internal temperature was adjusted to 170 ° C., and the degree of decompression was adjusted to 13.4 kPa over 30 minutes. Then, the degree of decompression was adjusted to 3.4 kPa over 20 minutes, and the temperature was maintained for 10 minutes. Further, the degree of decompression was adjusted to 0.9 kPa over 30 minutes, the internal temperature of the resin was adjusted to 180 ° C., and the temperature was maintained at that temperature for 10 minutes, then the degree of vacuum was set to 0.2 kPa, and the resin temperature was changed from 180 ° C. to 225 ° C. for 30 minutes. After reaching the specified viscosity, the mixture was discharged under nitrogen pressure from the bottom of the reaction vessel, and while cooling in the water vessel, the pellet was cut with a pelletizer to obtain pellets (ISS-PC2).

(Aspect 1 of the present invention)
[Example 1]
<Manufacturing of resin composition>
Using (ISS-PC1) and (ISS-PC2) obtained by the above-mentioned production of the polycarbonate resin (A) and the polycarbonate resin (B), and the acrylic resin (C), each resin was prepared at 90 ° C. for 12 After drying for more than an hour, the mixture is mixed so that the weight ratio is 40:20:40, and then melt-kneaded at 250 ° C. for both the cylinder and the die by a vent type twin-screw extruder [KZW15-25MG manufactured by Technobel Co., Ltd.]. Then, a resin composition pellet (P-1) of an acrylic resin and a polycarbonate resin was obtained.
<Manufacturing of film>
Using the resin composition pellet (P-1) prepared by the above production method, the screw diameter is 40 m.
The film was melted by a single-screw extruder of m and extruded through a T-type die having a set temperature of 230 ° C., and the extruded film was cooled by a mirror-finished roll to obtain a film of 100 μm. Table 1 shows various evaluation results of the obtained films.

[Example 2]
<Manufacturing of resin composition>
Resin composition pellets (P-2) in the same manner as in Example 1 except that (ISS-PC1), (ISS-PC2) and the acrylic resin (C) were mixed so as to have a weight ratio of 40:10:50. ) Was obtained.
<Manufacturing of film>
Except for the fact that (P-2) was used for the resin composition pellets, the same operation as in Example 1 was carried out, and the same evaluation was carried out. The results are shown in Table 1.

[Example 3]
<Manufacturing of resin composition>
Resin composition pellets (P-3) in the same manner as in Example 1 except that (ISS-PC1), (ISS-PC2) and the acrylic resin (C) were mixed so as to have a weight ratio of 30:20:50. ) Was obtained.
<Manufacturing of film>
Except for the fact that (P-3) was used for the resin composition pellets, the same operation as in Example 1 was carried out, and the same evaluation was carried out. The results are shown in Table 1.

[Example 4]
<Manufacturing of film>
In Example 3, the thickness of the extruded film was adjusted to obtain a film of 158 μm. Various evaluations of the obtained film were performed, and the results are shown in Table 1.

[Example 5]
<Manufacturing of resin composition>
Resin composition pellets (P-4) in the same manner as in Example 1 except that (ISS-PC1), (ISS-PC2) and the acrylic resin (C) were mixed so as to have a weight ratio of 20:30:50. ) Was obtained.
<Manufacturing of film>
Except for the fact that (P-4) was used for the resin composition pellets, the same operation as in Example 1 was carried out, and the same evaluation was carried out. The results are shown in Table 1.

[Example 6]
<Manufacturing of resin composition>
Resin composition pellets (P-5) in the same manner as in Example 1 except that (ISS-PC1), (ISS-PC2) and the acrylic resin (C) were mixed so as to have a weight ratio of 30:30:40. ) Was obtained.
<Manufacturing of film>
Except for the fact that (P-5) was used for the resin composition pellets, the same operation as in Example 1 was carried out, and the same evaluation was carried out. The results are shown in Table 1.

[Example 7]
<Manufacturing of resin composition>
Resin composition pellets (P-6) in the same manner as in Example 6 except that (ISS-PC1), (ISS-PC2) and the acrylic resin (C) were mixed so as to have a weight ratio of 50:20:30. ) Was obtained.
<Manufacturing of film>
Using (P-6) for the resin composition pellets, the same operation as in Example 1 was carried out to obtain a 94 μm film. The same evaluation as in Example 1 was performed, and the results are shown in Table 1.

[Example 8]
<Manufacturing of resin composition>
Resin composition pellets (P-7) in the same manner as in Example 6 except that (ISS-PC1), (ISS-PC2) and the acrylic resin (C) were mixed so as to have a weight ratio of 65:20:15. ) Was obtained.
<Manufacturing of film>
Using (P-7) as the resin composition pellet, the same operation as in Example 1 was carried out to obtain a 92 μm film. The same evaluation as in Example 1 was performed, and the results are shown in Table 1.

[Example 9]
<Manufacturing of resin composition>
Resin composition pellets (P-8) were obtained in the same manner as in Example 1 except that (ISS-PC1) and (ISS-PC2) were mixed so as to have a weight ratio of 70:30.
<Manufacturing of film>
Except for the fact that (P-8) was used for the resin composition pellets, the same operation as in Example 1 was carried out, and the same evaluation was carried out. The results are shown in Table 1.

[Example 10]
<Manufacturing of resin composition>
Resin composition pellets (P-9) were obtained in the same manner as in Example 1 except that (ISS-PC1) and (ISS-PC2) were mixed so as to have a weight ratio of 50:50.
<Manufacturing of film>
Except for the fact that (P-9) was used for the resin composition pellets, the same operation as in Example 1 was carried out, and the same evaluation was carried out. The results are shown in Table 1.

[Example 11]
<Manufacturing of film>
In Example 10, the thickness of the extruded film was adjusted to obtain a film of 168 μm. Various evaluations of the obtained film were performed, and the results are shown in Table 1.

[Example 12]
<Manufacturing of resin composition>
Resin composition pellets (P-10) were obtained in the same manner as in Example 1 except that (ISS-PC1) and (ISS-PC2) were mixed so as to have a weight ratio of 60:40.
<Manufacturing of film>
Using (P-10) as the resin composition pellet, the same operation as in Example 11 was carried out to obtain a 159 μm film. Various evaluations of the obtained film were performed, and the results are shown in Table 1.

[Example 13]
<Manufacturing of film>
In Example 9, the thickness of the extruded film was adjusted to obtain a film of 157 μm. Various evaluations of the obtained film were performed, and the results are shown in Table 1.

[Comparative Example 1]
<Manufacturing of film>
Except for the use of (ISS-PC1) pellets, the same operation as in Example 1 was carried out, and the same evaluation was performed. The results are shown in Table 1.

[Comparative Example 2]
Except for the use of (ISS-PC2) pellets, the same operation as in Example 1 was carried out, and the same evaluation was performed. The results are shown in Table 1.

[Comparative Example 3]
Except for the use of the acrylic resin (C) pellet, the same operation as in Example 1 was carried out, and the same evaluation was carried out. The results are shown in Table 1.

[Comparative Example 4]
<Manufacturing of resin composition>
A resin composition pellet (P-11) was obtained in the same manner as in Example 1 except that the weight ratio of (ISS-PC1) and the acrylic resin (C) was 50:50.
<Manufacturing of film>
Except for the fact that (P-11) was used for the resin composition pellets, the same operation as in Example 1 was carried out, and the same evaluation was carried out. The results are shown in Table 1.

[Comparative Example 5]
<Manufacturing of resin composition>
A resin composition pellet (P-12) was obtained in the same manner as in Example 1 except that the weight ratio of (ISS-PC1) and the acrylic resin (C) was 40:60.
<Manufacturing of film>
Except for the fact that (P-12) was used for the resin composition pellets, the same operation as in Example 1 was carried out, and the same evaluation was carried out. The results are shown in Table 1.

(Aspect 2 of the present invention)
[Example 14]
<Manufacturing of laminate>
Using polycarbonate (manufactured by Teijin Co., Ltd., trade name Panlite L-1225) as the thermoplastic resin, a resin composition pellet (P-1) prepared by a single-screw extruder with a screw diameter of 65 mm and the above manufacturing method can be used. Each of them is melted by a single-screw extruder with a screw diameter of 40 mm and laminated in two layers of two types by the multi-manifold method. The set temperature is 260 ° C. for polycarbonate resin and the set temperature for resin composition (P-1). Extruded through a T-shaped die at 230 ° C., and the obtained sheet was cooled with a mirror-finished roll to obtain a laminate. Further, at this time, the discharge amount of the molten resin was adjusted so that the thickness of each layer was about 50/250 (μm) of the first layer (resin composition layer) / second layer (polycarbonate layer). Table 2 shows various evaluation results of the obtained laminate.

[Example 15]
<Manufacturing of laminate>
Except that (P-2) was used for the resin composition pellet forming the first layer, exactly the same operation as in Example 14 was carried out, and the same evaluation was carried out. The results are shown in Table 2.

[Example 16]
<Manufacturing of laminate>
Except that (P-3) was used for the resin composition pellet forming the first layer, exactly the same operation as in Example 14 was carried out, and the same evaluation was carried out. The results are shown in Table 2.

[Example 17]
<Manufacturing of laminate>
Except that (P-4) was used for the resin composition pellet forming the first layer, exactly the same operation as in Example 14 was carried out, and the same evaluation was carried out. The results are shown in Table 2.

[Example 18]
<Manufacturing of laminate>
Except that (P-5) was used for the resin composition pellet forming the first layer, exactly the same operation as in Example 14 was carried out, and the same evaluation was carried out. The results are shown in Table 2.

[Example 19]
<Manufacturing of laminate>
Except that (P-6) was used for the resin composition pellet forming the first layer, exactly the same operation as in Example 14 was carried out, and the same evaluation was carried out. The results are shown in Table 2.

[Example 20]
<Manufacturing of laminate>
Except that (P-7) was used for the resin composition pellet forming the first layer, exactly the same operation as in Example 14 was carried out, and the same evaluation was carried out. The results are shown in Table 2.

[Example 21]
<Manufacturing of laminate>
Except that (P-8) was used for the resin composition pellet forming the first layer, exactly the same operation as in Example 14 was carried out, and the same evaluation was carried out. The results are shown in Table 2.

[Example 22]
<Manufacturing of laminate>
Except that (P-9) was used for the resin composition pellet forming the first layer, exactly the same operation as in Example 14 was carried out, and the same evaluation was carried out. The results are shown in Table 2.

[Example 23]
<Manufacturing of laminate>
Except that (P-10) was used for the resin composition pellet forming the first layer, exactly the same operation as in Example 14 was carried out, and the same evaluation was carried out. The results are shown in Table 2.

[Comparative Example 6]
<Manufacturing of laminate>
Except that (ISS-PC1) pellets were used for the resin composition pellets forming the first layer, exactly the same operation as in Example 14 was carried out, and the same evaluation was performed. The results are shown in Table 2.

[Comparative Example 7]
<Manufacturing of laminate>
Except that (ISS-PC2) pellets were used for the resin composition pellets forming the first layer, exactly the same operation as in Example 14 was carried out, and the same evaluation was performed. The results are shown in Table 2.

[Comparative Example 8]
<Manufacturing of laminate>
Except that the acrylic resin (C) pellet was used as the resin composition pellet forming the first layer, the same operation as in Example 14 was carried out, and the same evaluation was performed. The results are shown in Table 2.

[Comparative Example 9]
<Manufacturing of laminate>
Except that (P-11) was used for the resin composition pellet forming the first layer, exactly the same operation as in Example 14 was carried out, and the same evaluation was carried out. The results are shown in Table 2.

[Comparative Example 10]
<Manufacturing of laminate>
Except that (P-12) was used for the resin composition pellet forming the first layer, exactly the same operation as in Example 14 was carried out, and the same evaluation was carried out. The results are shown in Table 2.

The sheet or film and laminate of the present invention are excellent in transparency, chemical resistance, surface hardness, flexibility, and adhesion, and are transparent sheets for building materials, interior parts, display covers, etc., sheets for resin-coated metal plates, and molding. It is useful as a sheet for (vacuum / pressure molding, hot press molding, etc.), colored plate, transparent plate, shrink film, shrink label, shrink tube, automobile interior material, resin glazing, home appliance member, and OA equipment member.

Claims (13)

The repeating unit is from the unit (a) represented by the following formula (1), the unit (b) represented by the following formula (2), and the carbonate unit (c) other than the unit (a) and the unit (b). The repeating unit is the polycarbonate resin (A) containing 5 to 85 mol% of the unit (a), 15 to 95 mol% of the unit (b), and 0 to 80 mol% of the unit (c) among all the repeating units. It consists of a unit (a) represented by the following formula (1), a unit (b) represented by the following formula (2), and a carbonate unit (c) other than the unit (a) and the unit (b). Formed from a resin composition containing a polycarbonate resin (B) containing less than 5 mol% of the unit (a), 30 to 100 mol% of the unit (b), and 0 to 70 mol% of the unit (c) in the repeating unit. Sheet or film.

(In the formula, W represents an alkylene group having 1 to 20 carbon atoms or a cycloalkylene group having 6 to 20 carbon atoms, and R has a branched or linear alkyl group having 1 to 20 carbon atoms or a substituent. It represents a cycloalkyl group having 6 to 20 carbon atoms, and m represents an integer of 0 to 10.) The sheet or film according to claim 1, wherein the weight ratio of the polycarbonate resin (A) to the polycarbonate resin (B) is 5:95 to 95: 5. The sheet or film according to claim 1 or 2, wherein the resin composition further contains an acrylic resin (C). The sheet or film according to claim 3, wherein the total weight ratio of the polycarbonate resin (A) and the polycarbonate resin (B) to the acrylic resin (C) is 10:90 to 90:10. The sheet or film according to any one of claims 1 to 4, wherein the haze is 2.5% or less. The sheet or film according to any one of claims 1 to 5, wherein the thickness is 30 μm or more and 500 μm or less. A laminate formed from a sheet layer formed of a thermoplastic resin (D) and a film layer formed on at least one side of the sheet layer, and the repeating unit of the film layer is represented by the following formula (1). It is composed of a unit (a) to be formed, a unit (b) represented by the following formula (2), and a carbonate unit (c) other than the unit (a) and the unit (b). ) Is 5 to 85 mol%, the unit (b) is 15 to 95 mol%, the unit (c) is 0 to 80 mol%, and the repeating unit is represented by the following formula (1). It consists of (a), a unit (b) represented by the following formula (2), and a carbonate unit (c) other than the unit (a) and the unit (b), and the unit (a) is 5 among all repeating units. Less than mol%, unit (
A laminate which is a film layer formed from a resin composition containing a polycarbonate resin (B) containing 30 to 100 mol% of b) and 0 to 70 mol% of the unit (c).

(In the formula, W represents an alkylene group having 1 to 20 carbon atoms or a cycloalkylene group having 6 to 20 carbon atoms, and R has a branched or linear alkyl group having 1 to 20 carbon atoms or a substituent. It represents a cycloalkyl group having 6 to 20 carbon atoms, and m represents an integer of 0 to 10.) The laminate according to claim 7, wherein the weight ratio of the polycarbonate resin (A) to the polycarbonate resin (B) is 5:95 to 95: 5. The laminate according to claim 7 or 8, wherein the resin composition further contains an acrylic resin (C). The laminate according to claim 9, wherein the total weight ratio of the polycarbonate resin (A) and the polycarbonate resin (B) to the acrylic resin (C) is 10:90 to 90:10. The laminate according to any one of claims 7 to 10, wherein the haze is 1.0% or less. The laminate according to any one of claims 7 to 11, wherein the thickness of the film layer is 25 μm or more and 250 μm or less. The laminate according to any one of claims 7 to 12, wherein the thickness of the sheet layer is 100 μm or more and 500 μm or less.