WO2022118666A1

WO2022118666A1 - Laminate, fiber-reinforced plastic complex formed from laminate, and method for manufacturing fiber-reinforced plastic complex

Info

Publication number: WO2022118666A1
Application number: PCT/JP2021/042407
Authority: WO
Inventors: 幸介永田; 敦角田
Original assignee: 帝人株式会社
Priority date: 2020-12-01
Filing date: 2021-11-18
Publication date: 2022-06-09
Also published as: JPWO2022118666A1

Abstract

The present invention provides a laminate having exceptional adhesion with respect to reinforcing fibers, as well as exceptional rigidity, strength, and external appearance.　The present invention is a laminate of a strengthening fiber sheet and a thermoplastic resin sheet, wherein the laminate is characterized in that the thermoplastic resin sheet is formed from a resin composition containing 0.1-900 parts by weight of (C) a modified polyolefin resin (C component) per 100 parts by weight of a resin component comprising 1-99 parts by weight of (A) a polypropylene resin (A component) and 1-99 parts by weight of (B) a polycarbonate resin (B component), and the strengthening fiber content for strengthening fibers constituting the strengthening fiber sheet is 151-900 parts by weight per 100 parts by weight of the resin component comprising the A component and the B component.

Description

A method for producing a laminate, a fiber-reinforced resin composite composed of the laminate, and a fiber-reinforced resin composite.

The present invention relates to a laminate, a fiber-reinforced resin composite composed of the laminate, and a method for producing the fiber-reinforced resin composite. More specifically, it is excellent in rigidity, strength, low specific gravity and appearance, and is suitable for electric / electronic parts, home electric appliances, automobile-related parts, infrastructure-related parts, housing-related parts, etc. The present invention relates to a body and a method for producing a fiber-reinforced resin composite.

Fiber reinforced resin composites are used in a wide range of fields such as automobiles, aircraft parts, general industrial materials, etc. due to their light weight and high physical characteristics. Since these complexes are required to have surface appearance quality in addition to mechanical properties, it is necessary to sufficiently impregnate the reinforcing fibers with a resin and reduce voids and the like.

Thermosetting resin has been used as a matrix resin to sufficiently impregnate the reinforcing fiber with resin. On the other hand, thermoplastic resins are cheaper and have better impact resistance, heat resistance characteristics, and recyclability than thermosetting resins, but they are difficult to impregnate into reinforced fibers, and they are higher in temperature and pressure than thermosetting resins. It has not been widely used yet due to problems such as the need for molding.

Polypropylene resin has excellent molding processability and chemical resistance, and has a low specific gravity, so it is widely used industrially in electrical and electronic parts, home appliances, housings, packaging materials, automobile parts, and the like. Furthermore, in recent years, due to the demand for weight reduction of automobiles, it is widely used for automobile applications such as bumpers and interior / exterior parts. Therefore, various studies have been made so far, considering that a fiber-reinforced resin complex using polypropylene resin as a matrix resin can be a material having lightness, rigidity, and strength. However, since polypropylene resin does not have good adhesiveness to carbon fibers, sufficient mechanical properties cannot be obtained simply by laminating both. A composition containing a carbon fiber chopped strand having a fiber length of about 0.1 to 6 mm and a modified polypropylene grafted with an acid anhydride such as maleic anhydride has been proposed in order to improve the adhesiveness of the polypropylene resin. (Patent Documents 1 and 2). Further, a sizing agent used for a carbon fiber bundle containing a urethane-modified epoxy resin and an epoxy resin as main components has been proposed (Patent Document 3). Further, in order to improve the adhesiveness between the carbon fiber having a fiber length of about 1 to 6 mm and the polypropylene resin, it has been proposed to use a polypropylene resin containing a carboxylate bonded to a polymer chain (Patent Document 4).

These modified polyolefins react with functional groups such as carboxylic acid existing on the surface of the chopped strand-shaped carbon fiber during melt-kneading, and chemically bond the polyolefin to the surface of the carbon fiber to form a chopped strand-shaped carbon fiber. It is known to improve adhesion. However, in forming a complex with the sheet-shaped carbon fibers that does not go through melt-kneading, there is a problem that the adhesion to the sheet-shaped carbon fibers is insufficient, and as a result, the mechanical properties are insufficient.

On the other hand, in order to impart dimensional stability to polypropylene resin having insufficient dimensional stability, it has been proposed to blend and melt-knead a polycarbonate resin having excellent dimensional stability. At that time, in order to improve the compatibility between the polypropylene resin and the polycarbonate resin, it has been proposed to contain carbon milled fiber having a specific surface property (Patent Document 5). According to this proposal, the adhesiveness between the carbon milled fiber and the resin component is improved. However, in forming a complex with the sheet-shaped carbon fibers that does not go through melt-kneading, there is a problem that the adhesion to the sheet-shaped carbon fibers is insufficient, and as a result, the mechanical properties are insufficient. Further, it is known that the adhesiveness is improved by adding the polycarbonate resin to the polypropylene resin (Patent Document 6). However, in order to replace products in which metals and thermosetting CFRP are used and expand their applications, further strength, rigidity and high appearance are required.

Japanese Unexamined Patent Publication No. 55-50041 Japanese Unexamined Patent Publication No. 58-11239 Japanese Unexamined Patent Publication No. 61-252371 Japanese Unexamined Patent Publication No. 2010-150359 Japanese Unexamined Patent Publication No. 2016-22774 Japanese Patent No. 6744414

An object of the present invention is to solve the above problems and to obtain a laminate having excellent adhesion between a thermoplastic resin and a reinforcing fiber and having excellent rigidity, strength and appearance, and a fiber reinforced resin composite composed of the laminate.

As a result of diligent studies to solve such a problem, the present inventors have found that a thermoplastic resin sheet made of a polypropylene resin composition composed of a polypropylene resin, a polycarbonate resin and a modified polyolefin resin is not formed when laminated with a reinforcing fiber sheet. We have found that it is possible to obtain a fiber-reinforced resin composite having excellent rigidity, strength and appearance without causing layered peeling or significant deterioration of physical properties due to compatibility, and have reached the present invention.

That is, according to the present invention, (1) a laminate of a reinforcing fiber sheet and a thermoplastic resin sheet, wherein the thermoplastic resin sheet is (A) 1 to 99 parts by weight of a polypropylene resin (A component) and (B). ) A resin composition containing 0.1 to 900 parts by weight of (C) modified polyolefin resin (C component) with respect to 100 parts by weight of the resin component consisting of 99 to 1 part by weight of the polycarbonate resin (B component) and reinforced. Provided is a laminate characterized in that the content of the reinforcing fiber constituting the fiber sheet is 151 to 900 parts by weight with respect to 100 parts by weight of the resin component composed of the A component and the B component.
One of the more preferable embodiments of the present invention is the above-mentioned configuration (1) in which (2) the B component is a polycarbonate resin containing 1 to 100 mol% of the carbonate constituent units represented by the following formula [1] in the total carbonate constituent units. ).

[In the above general formula [1], R ¹ and R ² are independently hydrogen atom, halogen atom, alkyl group having 1 to 18 carbon atoms, alkoxy group having 1 to 18 carbon atoms, and 6 to 6 carbon atoms, respectively. 20 cycloalkyl groups, cycloalkoxy groups with 6 to 20 carbon atoms, alkenyl groups with 2 to 10 carbon atoms, aryl groups with 6 to 14 carbon atoms, aryloxy groups with 6 to 14 carbon atoms, carbon atoms Represents a group selected from the group consisting of an aralkyl group having a number of 7 to 20 and an aralkyloxy group having 7 to 20 carbon atoms, a nitro group, an aldehyde group, a cyano group and a carboxyl group. It may be different, where a and b are integers of 1 to 4, respectively, and W is at least one group selected from the group consisting of a single bond or a group represented by the following general formula [2].

(In the above general formula [2], R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ , R ¹⁷ and R ¹⁸ are independently hydrogen atoms, alkyl groups having 1 to 18 carbon atoms, and carbon atoms, respectively. Represents a group selected from the group consisting of an aryl group having a number of 6 to 14 and an aralkyl group having a carbon atom number of 7 to 20, and R ¹⁹ and R ²⁰ independently represent a hydrogen atom, a halogen atom, and an alkyl having 1 to 18 carbon atoms. Group, alkoxy group with 1 to 10 carbon atoms, cycloalkyl group with 6 to 20 carbon atoms, cycloalkoxy group with 6 to 20 carbon atoms, alkenyl group with 2 to 10 carbon atoms, 6 to 14 carbon atoms A group consisting of an aryl group, an aryloxy group having 6 to 10 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, an aralkyloxy group having 7 to 20 carbon atoms, a nitro group, an aldehyde group, a cyano group and a carboxyl group. Represents a group selected from, and R ²¹ , R ²² , R ²³ , R ²⁴ , R ²⁵ and R ²⁶ are independently hydrogen atoms, alkyl groups having 1 to 12 carbon atoms, or substituted or unsubstituted groups having 6 to 12 carbon atoms, respectively. If there are a plurality of aryl groups, they may be the same or different, c is an integer of 1 to 10, d is an integer of 4 to 7, e is a natural number, and f is 0 or a natural number. Yes, e + f is a natural number of 150 or less, and X is a divalent aliphatic group having 2 to 8 carbon atoms.)]
One of the more preferable embodiments of the present invention is the laminate according to the above configuration (1) or (2), wherein the component (3) C is maleic anhydride-modified polypropylene.

One of the more preferable embodiments of the present invention is a resin in which (4) the resin composition constituting the thermoplastic resin sheet further comprises (D) a styrene-based thermoplastic elastomer (component D) as a component A and a component B. The laminate according to any one of the above configurations (1) to (3), which is characterized by containing 1 to 20 parts by weight with respect to 100 parts by weight of the component.

One of the more preferable embodiments of the present invention is described in any one of the above configurations (1) to (4), wherein the (5) reinforcing fiber sheet is any one of a woven or knitted fabric, a non-woven fabric, and a unidirectional sheet. It is a laminated body.

One of the more preferable embodiments of the present invention is the above-mentioned configurations (1) to (5), wherein the fibers constituting the reinforcing fiber sheet (6) are at least one fiber selected from the group consisting of carbon fibers and glass fibers. ) Is the laminated body described in any one of.

One of the more preferable embodiments of the present invention is (7) the number of atoms of oxygen (O) and carbon (C) on the fiber surface measured by X-ray photoelectron spectroscopy in the fiber constituting the reinforcing fiber sheet. The laminate according to the above configuration (6), which is a carbon fiber having a surface oxygen concentration (O / C) of 0.15 or more, which is the ratio of the above.

One of the more preferable embodiments of the present invention is the laminate according to any one of the above configurations (1) to (7), wherein the (8) thermoplastic resin sheet is made of a mesh-like hollow fiber. ..

One of the more preferable embodiments of the present invention is (9) a fiber-reinforced resin complex composed of the laminate according to any one of the above configurations (1) to (8).

One of the more preferable embodiments of the present invention is to reinforce (10) the laminate according to any one of the above configurations (1) to (8) at a temperature equal to or higher than the melting temperature of the thermoplastic resin constituting the thermoplastic resin sheet. This is a method for producing a fiber-reinforced resin composite, which comprises pressure-treating at a temperature lower than the heat-resistant temperature of the reinforcing fibers constituting the fiber sheet.

The laminate of the present invention is a material having high flexibility and excellent followability to molds and the like. In addition, the fiber reinforced resin composite obtained by heat-pressurizing this laminate has excellent strength, rigidity and appearance, and is excellent in electric / electronic parts, household electrical appliances, automobile-related parts, infrastructure-related parts, and housing-related parts. It is useful for such purposes, and its industrial effect is exceptional.

It is a schematic diagram of the sectional view of the hollow fiber used in this invention. A cross-sectional view of the hollow fiber used in the present invention is taken with an electron microscope. It is a schematic diagram which shows the measuring method of the atypia of the hollow fiber used in this invention. It is a schematic diagram of the sectional view of the laminated body of this invention. It is a schematic diagram of the sectional view of the fiber reinforced resin composite of this invention.

Hereinafter, the present invention will be specifically described.
<Laminated body>
(Component A: polypropylene resin)
The polypropylene resin used as the component A of the polypropylene resin composition constituting the thermoplastic resin sheet in the present invention is a polymer of propylene, but in the present invention, a copolymer with other monomers is also included. An example of the polypropylene resin of the present invention is a homopolypropylene resin. Further, a block copolymer of propylene and ethylene, a block copolymer of propylene and an α-olefin having 4 to 10 carbon atoms (also referred to as “block polypropylene”), a random copolymer of propylene and ethylene, and propylene. It contains a random copolymer (also referred to as "random polypropylene") of α-olefin having 4 to 10 carbon atoms. In addition, "block polypropylene" and "random polypropylene" are collectively referred to as "polypropylene copolymer".

In the present invention, one or more of the above-mentioned homopolypropylene resin, block polypropylene, and random polypropylene may be used as the polypropylene resin, and homopolypropylene and block polypropylene are preferable. The polypropylene resin does not contain the modified polypropylene resin which is the C component.

Examples of α-olefins having 4 to 10 carbon atoms used in polypropylene copolymers include 1-butene, 1-pentene, isobutylene, 3-methyl-1-butene, 1-hexene, 3,4-dimethyl-1. -Butene, 1-heptene, 3-methyl-1-hexene are included.

The ethylene content in the polypropylene copolymer is preferably 5% by weight or less in all the monomers. The content of the α-olefin having 4 to 10 carbon atoms in the polypropylene copolymer is preferably 20% by weight or less in the total monomer.

The polypropylene copolymer is preferably a copolymer of propylene and ethylene, or a copolymer of propylene and 1-butene, and particularly preferably a copolymer of propylene and ethylene.

The melt flow rate (230 ° C., 2.16 kg) of the polypropylene resin in the present invention is preferably 0.1 to 5 g / 10 min, more preferably 0.2 to 4 g / 10 min, and 0.3 to 0.3 to. It is particularly preferable that it is 3 g / 10 min. If the melt flow rate of the polypropylene resin is less than 0.1 g / 10 min, the moldability is poor due to the high viscosity, and if it exceeds 5 g / 10 min, sufficient toughness may not be exhibited. The melt flow rate is also called "MFR". MFR was measured according to ISO1133.
(B component: polycarbonate resin)
Examples of the polycarbonate resin used as the B component of the resin composition constituting the thermoplastic resin sheet include those obtained by reacting a dihydroxy compound and a carbonate precursor by an interfacial polycondensation method or a melt transesterification method. .. In addition, those obtained by polymerizing a carbonate prepolymer by a solid phase transesterification method or those obtained by polymerizing a cyclic carbonate compound by a ring-opening polymerization method can be mentioned.

The dihydroxy component used here may be any as long as it is usually used as the dihydroxy component of aromatic polycarbonate, and may be bisphenols or aliphatic diols. As the bisphenols, bisphenols represented by the following formula [3] are preferably used.

[In the above general formula [3], R ¹ and R ² are independently hydrogen atom, halogen atom, alkyl group having 1 to 18 carbon atoms, alkoxy group having 1 to 18 carbon atoms, and 6 carbon atoms. ~ 20 cycloalkyl groups, 6-20 carbon atoms cycloalkoxy groups, 2-10 carbon atoms alkenyl groups, 6-14 carbon atoms aryl groups, 6-14 carbon atoms aryloxy groups, carbon Represents a group selected from the group consisting of an aralkyl group having 7 to 20 atoms, an aralkyloxy group having 7 to 20 carbon atoms, a nitro group, an aldehyde group, a cyano group and a carboxyl group, and if there are a plurality of each, they are the same. However, they may be different, and a and b are integers of 1 to 4, respectively, and W is at least one group selected from the group consisting of a single bond or a group represented by the following general formula [2].

(In the above general formula [2], R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ , R ¹⁷ and R ¹⁸ are independently hydrogen atoms, alkyl groups having 1 to 18 carbon atoms, and carbon. Represents a group selected from the group consisting of an aryl group having 6 to 14 atoms and an aralkyl group having 7 to 20 carbon atoms, and R ¹⁹ and R ²⁰ independently represent hydrogen atoms, halogen atoms, and carbon atoms 1 to 18 respectively. Alkyl group, alkoxy group with 1 to 10 carbon atoms, cycloalkyl group with 6 to 20 carbon atoms, cycloalkoxy group with 6 to 20 carbon atoms, alkenyl group with 2 to 10 carbon atoms, 6 carbon atoms From an aryl group of up to 14; an aryloxy group having 6 to 10 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, an aralkyloxy group having 7 to 20 carbon atoms, a nitro group, an aldehyde group, a cyano group and a carboxyl group. Represents a group selected from the group consisting of, R ²¹ , R ²² , R ²³ , R ²⁴ , R ²⁵ and R ²⁶ are each independently substituted with a hydrogen atom, an alkyl group having 1 to 12 carbon atoms or 6 to 12 carbon atoms. Alternatively, it is an unsubstituted aryl group, and if there are a plurality of them, they may be the same or different, c is an integer of 1 to 10, d is an integer of 4 to 7, e is a natural number, and f is a natural number. It is 0 or a natural number, e + f is a natural number of 150 or less, and X is a divalent aliphatic group having 2 to 8 carbon atoms.)]
Specific examples of bisphenols include, for example, 4,4'-dihydroxybiphenyl, bis (4-hydroxyphenyl) methane, 1,1-bis (4-hydroxyphenyl) ethane, and 1,1-bis (4-hydroxyphenyl). -1-phenylethane, 2,2-bis (4-hydroxyphenyl) propane, 2,2-bis (4-hydroxy-3-methylphenyl) propane, 1,1-bis (4-hydroxyphenyl) -3, 3,5-trimethylcyclohexane, 2,2-bis (4-hydroxy-3,3'-biphenyl) propane, 2,2-bis (4-hydroxy-3-isopropylphenyl) propane, 2,2-bis (3) -T-butyl-4-hydroxyphenyl) propane, 2,2-bis (4-hydroxyphenyl) butane, 2,2-bis (4-hydroxyphenyl) octane, 2,2-bis (3-bromo-4- Hydroxyphenyl) propane, 2,2-bis (3,5-dimethyl-4-hydroxyphenyl) propane, 2,2-bis (3-cyclohexyl-4-hydroxyphenyl) propane, 1,1-bis (3-cyclohexyl) -4-Hydroxyphenyl) cyclohexane, bis (4-hydroxyphenyl) diphenylmethane, 9,9-bis (4-hydroxyphenyl) fluorene, 9,9-bis (4-hydroxy-3-methylphenyl) fluorene, 1,1 -Bis (4-hydroxyphenyl) cyclohexane, 1,1-bis (4-hydroxyphenyl) cyclopentane, 4,4'-dihydroxydiphenylether, 4,4'-dihydroxy-3,3'-dimethyldiphenyle -Tell, 4,4'-sulfonyldiphenol, 4,4'-dihydroxydiphenylsulfooxide, 4,4'-dihydroxydiphenylsulfide, 2,2'-dimethyl-4,4'-sulfonyldiphenol, 4,4'-Dihydroxy-3,3'-dimethyldiphenylsulfoxide,4,4'-dihydroxy-3,3'-dimethyldiphenylsulfide,2,2'-diphenyl-4,4'-sulfonyldiphenol,4,4'-dihydroxy-3,3'-diphenyldiphenylsulfoxide,4,4'-dihydroxy-3,3'-diphenyldiphenylsulfide, 1,3-bis {2- (4-hydroxyphenyl) propyl} benzene, 1,4-bis { 2- (4-Hydroxyphenyl) propyl} benzene, 1,4-bis (4-hydroxyphenyl) cyclo Hexane, 1,3-bis (4-hydroxyphenyl) cyclohexane, 4,8-bis (4-hydroxyphenyl) tricyclo [5.2.1.02,6] decane, 4,4'-(1,3-_) Adamantane diyl) diphenol, 1,3-bis (4-hydroxyphenyl) -5,7-dimethyladamantan and the like can be mentioned.

Examples of the aliphatic diols include 2,2-bis- (4-hydroxycyclohexyl) -propane, 1,14-tetradecanediol, octaethyleneglycol, 1,16-hexadecanediol, and 4,4'-bis (2-). Hydroxyethoxy) biphenyl, bis {(2-hydroxyethoxy) phenyl} methane, 1,1-bis {(2-hydroxyethoxy) phenyl} ethane, 1,1-bis {(2-hydroxyethoxy) phenyl} -1- Phenylethane, 2,2-bis {(2-hydroxyethoxy) phenyl} propane, 2,2-bis {(2-hydroxyethoxy) -3-methylphenyl} propane, 1,1-bis {(2-hydroxyethoxy) ) Penyl} -3,3,5-trimethylcyclohexane, 2,2-bis {4- (2-hydroxyethoxy) -3,3'-biphenyl} propane, 2,2-bis {(2-hydroxyethoxy)- 3-Isopropyl} propane, 2,2-bis {3-t-butyl-4- (2-hydroxyethoxy) phenyl} propane, 2,2-bis {(2-hydroxyethoxy) phenyl} butane, 2,2 -Bis {(2-hydroxyethoxy) phenyl} -4-methylpentane, 2,2-bis {(2-hydroxyethoxy) phenyl} octane, 1,1-bis {(2-hydroxyethoxy) phenyl} decane, 2 , 2-bis {3-bromo-4- (2-hydroxyethoxy) phenyl} propane, 2,2-bis {3,5-dimethyl-4- (2-hydroxyethoxy) phenyl} propane, 2,2-bis {3-Cycloxy-4- (2-hydroxyethoxy) phenyl} propane, 1,1-bis {3-cyclohexyl-4- (2-hydroxyethoxy) phenyl} cyclohexane, bis {(2-hydroxyethoxy) phenyl} diphenylmethane , 9,9-bis {(2-hydroxyethoxy) phenyl} fluorene, 9,9-bis {4- (2-hydroxyethoxy) -3-methylphenyl} fluorene, 1,1-bis {(2-hydroxyethoxy) ) Benz} cyclohexane, 1,1-bis {(2-hydroxyethoxy) phenyl} cyclopentane, 4,4'-bis (2-hydroxyethoxy) diphenylether, 4,4'-bis (2-hydroxyethoxy) ) -3,3'-dimethyldiphenyl ether, 1,3-bis [2-{(2-hydroxyethoxy) phenyl} propyl] benzene, 1,4-bis [2-{(2-hydroxyethoxy) phenyl} propyl] benzene, 1,4-bis {(2-hydroxyethoxy) phenyl} cyclohexane, 1,3-bis {(2-hydroxyethoxy) phenyl } Cyclohexane, 4,8-bis {(2-hydroxyethoxy) phenyl} tricyclo [5.2.1.02,6] decane, 1,3-bis {(2-hydroxyethoxy) phenyl} -5,7- Dimethyladamantan, 3,9-bis (2-hydroxy-1,1-dimethylethyl) -2,4,8,10-tetraoxaspiro (5,5) undecane, 1,4: 3,6-dianhydro-D -Sorbitol (isosorbide), 1,4: 3,6-dianhydro-D-mannitol (isomannide), 1,4: 3,6-dianhydro-L-iditol (isoidid) and the like can be mentioned.

Among these, aromatic bisphenols are preferable, and among them, 1,1-bis (4-hydroxyphenyl) -1-phenylethane, 2,2-bis (4-hydroxyphenyl) propane, and 2,2-bis (4). -Hydroxy-3-methylphenyl) propane, 1,1-bis (4-hydroxyphenyl) cyclohexane, 1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane, 4,4'-sulfonyl Diphenol, 2,2'-dimethyl-4,4'-sulfonyldiphenol, 9,9-bis (4-hydroxy-3-methylphenyl) fluorene, 1,3-bis {2- (4-hydroxyphenyl) Propyl} benzene and 1,4-bis {2- (4-hydroxyphenyl) propyl} benzene are preferred. In particular, 2,2-bis (4-hydroxyphenyl) propane, 1,1-bis (4-hydroxyphenyl) cyclohexane, 4,4'-sulfonyldiphenol and 9,9-bis (4-hydroxy-3-). Methylphenyl) fluorene is preferred. Of these, 2,2-bis (4-hydroxyphenyl) propane, which has excellent strength and good durability, is most suitable. Moreover, these may be used individually or in combination of 2 or more types.

The polycarbonate resin used as the B component of the present invention may be a branched polycarbonate resin by using a branching agent in combination with the above dihydroxy compound.

Examples of the trifunctional or higher polyfunctional aromatic compound used in such a branched polycarbonate resin include fluoroglucolcin, fluoroglucolside, 4,6-dimethyl-2,4,6-tris (4-hydrochidiphenyl) heptene-2,2. 4,6-trimethyl-2,4,6-tris (4-hydroxyphenyl) heptane, 1,3,5-tris (4-hydroxyphenyl) benzene, 1,1,1-tris (4-hydroxyphenyl) ethane , 1,1,1-Tris (3,5-dimethyl-4-hydroxyphenyl) ethane, 2,6-bis (2-hydroxy-5-methylbenzyl) -4-methylphenol, 4- {4- [1 , 1-bis (4-hydroxyphenyl) ethyl] benzene} -α, α-dimethylbenzylphenol and other trisphenols. Further, tetra (4-hydroxyphenyl) methane, bis (2,4-dihydroxyphenyl) ketone, 1,4-bis (4,4-dihydroxytriphenylmethyl) benzene and the like can be mentioned. Examples thereof include trimellitic acid, pyromellitic acid, benzophenone tetracarboxylic acid and acid chlorides thereof. Of these, 1,1,1-tris (4-hydroxyphenyl) ethane and 1,1,1-tris (3,5-dimethyl-4-hydroxyphenyl) ethane are preferable, and 1,1,1-tris (4-hydroxyphenyl) ethane is particularly preferable. Hydroxyphenyl) ethane is preferred.

These polycarbonate resins are produced by a reaction method known per se for producing an ordinary aromatic polycarbonate resin, for example, a method of reacting an aromatic dihydroxy component with a carbonate precursor such as phosgene or carbonic acid diester. The basic means for the manufacturing method will be briefly described.

In a reaction using, for example, phosgene as a carbonate precursor, the reaction is usually carried out in the presence of an acid binder and a solvent. As the acid binder, for example, an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide or an amine compound such as pyridine is used. As the solvent, for example, halogenated hydrocarbons such as methylene chloride and chlorobenzene are used. Further, for example, a catalyst such as a tertiary amine or a quaternary ammonium salt can be used to promote the reaction. At that time, the reaction temperature is usually 0 to 40 ° C., and the reaction time is several minutes to 5 hours. The transesterification reaction using a carbonic acid diester as a carbonic acid precursor is carried out by a method of distilling off the produced alcohol or phenol by stirring a predetermined ratio of aromatic dihydroxy components with the carbonic acid diester while heating them in an inert gas atmosphere. .. 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. It is also possible to use catalysts normally used in transesterification reactions to accelerate the reaction. Examples of the carbonic acid diester used in the transesterification reaction include diphenyl carbonate, dinaphthyl carbonate, bis (diphenyl) carbonate, dimethyl carbonate, diethyl carbonate, dibutyl carbonate and the like. Of these, diphenyl carbonate is particularly preferable.

A terminal inhibitor may be used in the polymerization reaction. The terminal terminator is used for molecular weight regulation, and the obtained polycarbonate resin has a closed end, so that it is superior in thermal stability as compared with the non-termination agent. As such a terminal terminator, monofunctional phenols represented by the following general formulas [4] to [6] can be shown.

[In the formula, A is a hydrogen atom, an alkyl group having 1 to 9 carbon atoms, an alkylphenyl group (the number of carbon atoms in the alkyl moiety is 1 to 9), a phenyl group, or a phenylalkyl group (the number of carbon atoms in the alkyl moiety is 1 to 9). R is an integer of 1 to 5, preferably 1 to 3. ]

[In the formula, Y is -RO-, -R-CO-O- or -RO-CO-, where R is a single bond or 1 to 10 carbon atoms, preferably 1 to 5 carbon atoms. It represents a divalent aliphatic hydrocarbon group, and n represents an integer of 10 to 50. ]
Specific examples of the monofunctional phenols represented by the above general formula [4] include, for example, phenol, isopropylphenol, p-tert-butylphenol, p-cresol, p-cumylphenol, 2-phenylphenol, 4-phenyl. Examples include phenol and isooctylphenol.

Further, the monofunctional phenols represented by the above general formulas [5] to [6] are phenols having a long-chain alkyl group or an aliphatic ester group as a substituent, and these are used to end the polycarbonate resin. When sealed, they not only function as a terminal terminator or a molecular weight modifier, but also improve the melt fluidity of the resin, facilitate the molding process, and have the effect of lowering the water absorption rate of the resin, which is preferable. used.

As the substituted phenols of the above general formula [5], those having n of 10 to 30, particularly 10 to 26 are preferable. Specific examples thereof include decylphenol, dodecylphenol, tetradecylphenol, hexadecylphenol, octadecylphenol, eicosylphenol, docosylphenol, and triacylphenol.

Further, as the substituted phenols of the above general formula [6], compounds in which Y is —R—CO—O— and R is a single bond are preferable, and n is 10 to 30, particularly 10 to 26. Suitable. Specific examples thereof include decyl hydroxybenzoate, dodecyl hydroxybenzoate, tetradecyl hydroxybenzoate, hexadecyl hydroxybenzoate, eikosyl hydroxybenzoate, docosyl hydroxybenzoate and triacontyl hydroxybenzoate.

Among these monofunctional phenols, monofunctional phenols represented by the above general formula [4] are preferable, alkyl-substituted or phenylalkyl-substituted phenols are more preferable, and p-tert-butylphenol and p are particularly preferable. -Kumilphenol or 2-phenylphenol. It is desirable that the terminal terminator of these monofunctional phenols be introduced into the terminal at least 5 mol%, preferably at least 10 mol% with respect to the total terminal of the obtained polycarbonate resin, and the terminal terminator is used alone. Or a mixture of two or more types may be used.

The polycarbonate resin used as the B component of the present invention may be a polyester carbonate obtained by copolymerizing an aromatic dicarboxylic acid, for example, terephthalic acid, isophthalic acid, naphthalenedicarboxylic acid or a derivative thereof, as long as the gist of the present invention is not impaired. good.

The viscosity average molecular weight of the polycarbonate resin used as the component B of the present invention is preferably in the range of 13,000 to 25,000, more preferably 13,000 to 21,000, and further preferably in the range of 16,000 to 21,000. More preferably, the range of 16,000 to 20,000 is most preferable. If the molecular weight exceeds 25,000, the melt viscosity may become too high and the moldability may be inferior, and if the molecular weight is less than 13,000, a problem may occur in mechanical strength. The viscosity average molecular weight referred to in the present invention was obtained by first determining the specific viscosity calculated by the following formula from a solution of 0.7 g of polycarbonate resin in 100 ml of methylene chloride using an Ostwald viscometer. The specific viscosity is inserted by the following formula to obtain the viscosity average molecular weight M.

Specific viscosity (η _SP ) = (t-t ₀ ) / t ₀
[T ₀ is the number of seconds for methylene chloride to fall, and t is the number of seconds for the sample solution to fall]
η _SP / c = [η] +0.45 × [η] ² c (however, [η] is the ultimate viscosity)
[Η] = 1.23 × 10 ^-4 M ^0.83
c = 0.7
The total amount of Cl (chlorine) in the polycarbonate resin used as the component B of the present invention is preferably 0 to 200 ppm, more preferably 0 to 150 ppm. If the total amount of Cl in the polycarbonate resin exceeds 200 ppm, the hue and thermal stability may deteriorate, which is not preferable.

The content of the B component is 99 to 1 part by weight, preferably 50 to 5 parts by weight, more preferably 25 to 5 parts by weight, and most preferably 15 to 15 parts by weight in 100 parts by weight of the total of the A component and the B component. 5 parts by weight. If the B component is more than 99 parts by weight, the appearance improvement when the fiber reinforced resin composite is formed is insufficient. Further, when the B component is less than 1 part by weight, the adhesion between the resin and the reinforcing fiber is lowered, the strength of the fiber-reinforced composite is not sufficiently developed, and the appearance is not sufficiently improved.
(C component: modified polyolefin resin)
The resin composition constituting the thermoplastic resin sheet contains a modified polyolefin resin as a compatibilizer. The modified polyolefin resin improves the interfacial adhesion between the polypropylene resin and the reinforcing fiber, and improves the strength of the fiber-reinforced resin composite.

The modified polyolefin resin is preferably an acid-modified polyolefin resin modified with an unsaturated carboxylic acid or a derivative thereof. Examples of the modified polyolefin resin include polyethylene resin and polypropylene resin, and polypropylene resin is preferable. The modified polypropylene resin includes a propylene homopolymer, a propylene random copolymer, a propylene block copolymer and the like. For the modification of the polyolefin resin, a method such as graft modification or copolymerization can be used.

Examples of the unsaturated carboxylic acid used for modifying the polyolefin resin include acrylic acid, methacrylic acid, maleic acid, nadic acid, fumaric acid, itaconic acid, crotonic acid, citraconic acid, sorbic acid, mesaconic acid, angelic acid and the like. Can be mentioned. Derivatives of the unsaturated carboxylic acid include acid anhydrides, esters, amides, imides, metal salts and the like. For example, maleic anhydride, itaconic anhydride, citraconic anhydride, nadic acid anhydride, methyl acrylate, methyl methacrylate, ethyl acrylate, butyl acrylate, monoethyl maleic acid ester, acrylamide, maleic acid monoamide, maleimide, N- Examples thereof include butylmaleimide, sodium acrylate, sodium methacrylate and the like. Among these, unsaturated dicarboxylic acids and derivatives thereof are preferable, and maleic anhydride or phthalic anhydride is particularly preferable.

The crystallization temperature (Tc) of the modified polypropylene resin is preferably 90 to 125 ° C, more preferably 110 to 120 ° C. The ultimate viscosity is preferably 0.1 to 2.4 dl / g, preferably 0.2 to 1.6 dl / g. The crystallization temperature (Tc) of the modified polyolefin resin can be measured by a differential scanning calorimeter (DSC). The ultimate viscosity of the modified polyolefin resin can be measured in tetralin at 135 ° C. The amount of carboxylic acid added to the modified polyolefin resin is preferably in the range of 0.1 to 14% by weight, more preferably in the range of 0.8 to 8% by weight. The acid addition amount can be determined from the area of the peak of 1670 cm ^-1 to 1810 cm ^-1 by measuring the IR spectrum of the acid-modified polyolefin resin.

The content of the modified polyolefin resin is 0.1 to 900 parts by weight, preferably 1 to 500 parts by weight, and more preferably 5 to 300 parts by weight with respect to 100 parts by weight of the total of the components A and B. It is more preferably 50 to 150 parts by weight. If the content of the modified polyolefin resin is less than 0.1 parts by weight, the strength of the fiber reinforced resin composite does not improve, and if it exceeds 900 parts by weight, the sheet processability deteriorates. It is not sufficiently expressed and the appearance is not sufficiently improved.
(D component: styrene-based thermoplastic elastomer)
A styrene-based thermoplastic elastomer can be further added to the resin composition constituting the thermoplastic resin sheet. The styrene-based thermoplastic elastomer improves the compatibility between the polypropylene resin and the polycarbonate resin, and improves the strength (bending elastic modulus, bending strength) of the fiber-reinforced resin composite.

Examples of the styrene-based thermoplastic elastomer include styrene-ethylene-butylene-styrene block copolymer, styrene-hydrogenated butadiene-styrene triblock copolymer, styrene-isoprene-styrene triblock copolymer, and styrene-hydrogenated isoprene-. Examples thereof include styrene triblock copolymers, styrene-hydrogenated butadiene diblock copolymers, styrene-hydrogenated isoprange block copolymers, styrene-isopresend block copolymers, etc., among which styrene-ethylene-butylene- The styrene block copolymer is most suitable.

Further, a block copolymer represented by the following formula (I) or (II) is also preferably used.
X- (YX) _n ... (I)
(XY) _n ... (II)
X in the general formulas (I) and (II) is a styrene polymer block, and in the formula (I), the degree of polymerization may be the same or different at both ends of the molecular chain. Y is at least one selected from an isoprene polymer block, a hydrogenated butadiene polymer block and a hydrogenated isoprene polymer block. Further, n is an integer of 1 or more.

The content of the X component in the block copolymer is preferably in the range of 20 to 80% by weight, more preferably 25 to 70% by weight. If this amount is less than 20% by weight, the rigidity of the resin composition tends to decrease. Further, if it exceeds 80% by weight, the molding processability and the impact strength tend to decrease. Specific examples of such block copolymers include styrene-hydrogenated butadiene-styrene triblock copolymer, styrene-isoprene-styrene triblock copolymer, styrene-hydrogenated isoprene-styrene triblock copolymer, and the like. Examples thereof include a styrene-hydrogenated butadiene diblock copolymer, a styrene-hydrogenated isoprange block copolymer, and a styrene-isoprerange block copolymer.

The weight average molecular weight of the styrene-based thermoplastic elastomer is preferably 250,000 or less, more preferably 220,000 or less, and even more preferably 200,000 or less. If the weight average molecular weight exceeds 250,000, the moldability is lowered and the dispersibility in the polypropylene resin may be deteriorated. The lower limit of the weight average molecular weight is not particularly limited, but is preferably 40,000 or more, and more preferably 50,000 or more. The weight average molecular weight was measured by the following method. That is, the molecular weight is measured in terms of polystyrene by a gel permeation chromatograph, and the weight average molecular weight is calculated.

The content of the styrene-based thermoplastic elastomer is preferably 1 to 20 parts by weight, more preferably 3 to 15 parts by weight, still more preferably 5 to 13 parts by weight, most preferably 5 to 13 parts by weight, based on 100 parts by weight of the resin component. It is preferably 5 to 10 parts by weight. If the content of the styrene-based thermoplastic elastomer is less than 1 part by weight, the strength of the fiber-reinforced resin composite does not improve, and if it exceeds 20 parts by weight, gas is generated during molding of the fiber-reinforced resin composite, and the molding processability is improved. It may decrease.
(Other ingredients)
Various additives can be added to the resin composition constituting the thermoplastic resin sheet as long as the effects of the present invention are not impaired. Examples of such additives include phosphorus-based heat stabilizers, phenol-based heat stabilizers, sulfur-containing antioxidants, mold release agents, ultraviolet absorbers, hindered amine-based light stabilizers, compatibilizers, flame retardants, dyes and pigments. Be done. Hereinafter, these additives will be specifically described.
(Phosphorus heat stabilizer)
As the phosphorus-based heat stabilizer, any of a phosphite compound, a phosphonite compound, and a phosphate compound can be used.

Various phosphite compounds can be used. Specific examples thereof include a phosphite compound represented by the following general formula [7], a phosphite compound represented by the following general formula [8], and a phosphite compound represented by the following general formula [9].

[In the formula, R ³¹ is a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an alkaline phenol group having 6 to 20 carbon atoms, an aralkyl group having 7 to 30 carbon atoms, or these. It represents a halo, an alkylthio (alkyl group has 1 to 30 carbon atoms) or a hydroxy substituent, and the three R ^31s can be selected either identically or differently from each other, and are cyclic by being derived from divalent phenols. You can also choose the structure. ]

[In the formula, R ³² and R ³³ are hydrogen atoms, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an alkylaryl group having 6 to 20 carbon atoms, and an aralkyl group having 7 to 30 carbon atoms, respectively. , A cycloalkyl group having 4 to 20 carbon atoms and a 2- (4-oxyphenyl) propyl substituted aryl group having 15 to 25 carbon atoms. As the cycloalkyl group and the aryl group, either one which is not substituted with an alkyl group or one substituted with an alkyl group can be selected. ]

[In the formula, R ³⁴ and R ³⁵ are alkyl groups having 12 to 15 carbon atoms. In addition, R ³⁴ and R ³⁵ can be selected in either the same case or different from each other. ]
Examples of the phosphonite compound include a phosphonite compound represented by the following general formula [10] and a phosphonite compound represented by the following general formula [11].

[In the formula, Ar ¹ and Ar ² are aryl groups having 6 to 20 carbon atoms, alkyl aryl groups having 6 to 20 carbon atoms, or 2- (4-oxyphenyl) propyl substituted aryl groups having 15 to 25 carbon atoms. As shown, the four Ar ^1s can be selected to be the same as each other or different from each other. Alternatively, the two Ar ^2s can be selected to be the same as each other or different from each other. ]
Preferred specific examples of the phosphite compound represented by the above general formula [7] are diphenylisooctylphosphite, 2,2'-methylenebis (4,6-di-tert-butylphenyl) octylphosphite, and diphenylmono. Examples thereof include (tridecylic) phosphite, phenyldiisodecylphosphite, and phenyldi (tridecylic) phosphite.

Preferred specific examples of the phosphite compound represented by the above general formula [8] include distearyl pentaerythritol diphosphite, bis (2,4-di-tert-butylphenyl) pentaerythritol diphosphite, and bis (2). , 6-Di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite, phenylbisphenol A pentaerythritol diphosphite, dicyclohexylpentaerythritol diphosphite and the like. Preferred are distearyl pentaerythritol diphosphite, bis (2,4-di-tert-butylphenyl) pentaerythritol diphosphite, bis (2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphos. You can mention fight. The phosphite compound may be used alone or in combination of two or more.

As a preferable specific example of the phosphite compound represented by the above general formula [9], 4,4'-isopropyridene diphenol tetratridecylphosphite can be mentioned.

Preferred specific examples of the phosphonite compound represented by the above general formula [10] include tetrakis (2,4-di-iso-propylphenyl) -4,4'-biphenylenediphosphonite and tetrakis (2,4-di). -N-Butylphenyl) -4,4'-biphenylenediphosphonite, tetrakis (2,4-di-tert-butylphenyl) -4,4'-biphenylenediphosphonite, tetrakis (2,4-di-tert) -Butylphenyl) -4,3'-biphenylenediphosphonite, tetrakis (2,4-di-tert-butylphenyl) -3,3'-biphenylenediphosphonite, tetrakis (2,6-di-iso-propyl) Phenyl) -4,4'-biphenylenediphosphonite, tetrakis (2,6-di-n-butylphenyl) -4,4'-biphenylenediphosphonite, tetrakis (2,6-di-tert-butylphenyl) -4,4'-biphenirange phosphonite, tetrakis (2,6-di-tert-butylphenyl) -4,3'-biphenirange phosphonite, tetrakis (2,6-di-tert-butylphenyl) -3 , 3'-biphenylenediphosphonite and the like. Of these, tetrakis (di-tert-butylphenyl) -biphenylenediphosphonite is preferable, and tetrakis (2,4-di-tert-butylphenyl) -biphenylenediphosphonite is more preferable. The tetrakis (2,4-di-tert-butylphenyl) -biphenylenediphosphonite is preferably a mixture of two or more. Specifically, tetrakis (2,4-di-tert-butylphenyl) -4,4'-biphenylenediphosphonite, tetrakis (2,4-di-tert-butylphenyl) -4,3'-biphenylenedi One or more of phosphonite and tetrakis (2,4-di-tert-butylphenyl) -3,3'-biphenylenediphosphonite can be used in combination, but preferably three such types. It is a mixture.

Preferred specific examples of the phosphonite compound represented by the above general formula [11] include bis (2,4-di-iso-propylphenyl) -4-phenyl-phenylphosphonite and bis (2,4-di-n). -Butylphenyl) -3-Phenyl-Phenylphosphonite, bis (2,4-di-tert-butylphenyl) -4-phenyl-phenylphosphonite, bis (2,4-di-tert-butylphenyl) -3 -Phenyl-Phenylphosphonite bis (2,6-di-iso-propylphenyl) -4-phenyl-phenylphosphonite, bis (2,6-di-n-butylphenyl) -3-phenyl-phenylphosphonite, Examples thereof include bis (2,6-di-tert-butylphenyl) -4-phenyl-phenylphosphonite and bis (2,6-di-tert-butylphenyl) -3-phenyl-phenylphosphonite. Bis (di-tert-butylphenyl) -phenyl-phenylphosphonite is preferred, and bis (2,4-di-tert-butylphenyl) -phenyl-phenylphosphonite is more preferred.

This bis (2,4-di-tert-butylphenyl) -phenyl-phenylphosphonite is preferably a mixture of two or more. Specifically, one of bis (2,4-di-tert-butylphenyl) -4-phenyl-phenylphosphonite and bis (2,4-di-tert-butylphenyl) -3-phenyl-phenylphosphonite. Species or two species can be used in combination. It is preferably a mixture of the two. Further, in the case of a mixture of two kinds, the mixing ratio thereof is preferably in the range of 5: 1 to 4 in terms of weight ratio, and more preferably in the range of 5: 2 to 3.

On the other hand, as the phosphate compound, tributyl phosphate, trimethyl phosphate, tricresyl phosphate, triphenyl phosphate, trichlorophenyl phosphate, triethyl phosphate, diphenyl cresyl phosphate, diphenyl monoorthoxenyl phosphate, tributoxyethyl phosphate, dibutyl phosphate, dioctyl Examples thereof include phosphate and diisopropyl phosphate. It is preferably trimethyl phosphate.

Among the above phosphorus-based heat stabilizers, more preferable compounds include compounds represented by the following general formulas [12] and [13].

[In the formula [12], R ³⁶ and R ³⁷ each independently represent an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group, an aryl group or an aralkyl group. ]

[In the formula [13], R ⁴¹ , R ⁴² , R ⁴³ , R ⁴⁴ , R ⁴⁷ , R ⁴⁸ and R ⁴⁹ are independently hydrogen atoms, alkyl groups having 1 to 12 carbon atoms, cycloalkyl groups, respectively. An aryl group or an aralkyl group is indicated, R ⁴⁵ indicates a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R ⁴⁶ indicates a hydrogen atom or a methyl group. ]
In the formula [12], R ³⁶ and R ³⁷ are preferably an alkyl group having 1 to 12 carbon atoms, and more preferably an alkyl group having 1 to 8 carbon atoms.

Specific examples of the compound represented by the formula [12] include tris (dimethylphenyl) phosphite, tris (diethylphenyl) phosphite, tris (di-iso-propylphenyl) phosphite, and tris (di-n-butyl). Phenyl) Phenyl) Phenyl, Tris (2,4-di-tert-butylphenyl) Phenyl, Tris (2,6-di-tert-butylphenyl) Phenyl, Tris (2,6-di-tert-butylphenyl) Examples include phosphite. Particularly, tris (2,6-di-tert-butylphenyl) phosphite is preferable.

Specific examples of the compound represented by the formula [13] include phosphite derived from 2,2'-methylenebis (4,6-di-tert-butylphenol) and 2,6-di-tert-butylphenol, 2. , 2'-Methylenebis (4,6-di-tert-butylphenol) and phenol-derived phosphite. In particular, 2,2'-methylenebis (4,6-di-tert-butylphenol) and phosphite derived from phenol are preferable.

The content of the phosphorus-based heat stabilizer is preferably 0.001 to 3.0 parts by weight, more preferably 0.01 to 2.0 parts by weight, based on 100 parts by weight of the total of the A component and the B component. More preferably, it is 0.05 to 1.0 parts by weight. If the content of the phosphorus-based heat stabilizer is less than 0.001 part by weight, the mechanical properties may not be sufficiently exhibited, and if it exceeds 3.0 parts by weight, the mechanical properties may not be sufficiently exhibited.
(Phenolic heat stabilizer)
Examples of the phenolic heat stabilizer used in the present invention generally include hindered phenol, semi-hindered phenol, and less hindered phenol compound. In particular, a hindered phenol compound is more preferably used from the viewpoint of applying a heat-stable formulation to a polypropylene-based resin.

Specific examples of such hindered phenol compounds include vitamin E, n-octadecyl-β- (4'-hydroxy-3', 5'-di-tert-butylfell) propionate, and 2-tert-butyl-6. -(3'-tert-Butyl-5'-methyl-2'-hydroxybenzyl) -4-methylphenyl acrylate, 2,6-di-tert-butyl-4- (N, N-dimethylaminomethyl) phenol, 3,5-Di-tert-butyl-4-hydroxybenzylphosphonate diethyl ester, 2,2'-methylenebis (4-methyl-6-tert-butylphenol), 2,2'-methylenebis (4-ethyl-6-tert) -Butylphenol), 4,4'-methylenebis (2,6-di-tert-butylphenol), 2,2'-methylenebis (4-methyl-6-cyclohexylphenol), 2,2'-dimethylene-bis (6-- α-Methyl-benzyl-p-cresol) 2,2'-ethylidene-bis (4,6-di-tert-butylphenol), 2,2'-butylidene-bis (4-methyl-6-tert-butylphenol), 4,4'-butylidenebis (3-methyl-6-tert-butylphenol), triethylene glycol-N-bis-3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionate, 1,6- Hexandiol bis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, bis [2-tert-butyl-4-methyl 6- (3-tert-butyl-5-methyl-2) -Hydroxybenzyl) phenyl] terephthalate, 3,9-bis {2- [3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy] -1,1,-dimethylethyl} -2, 4,8,10-Tetraoxaspiro [5,5] undecane, 4,4'-thiobis (6-tert-butyl-m-cresol), 4,4'-thiobis (3-methyl-6-tert-butylphenol) ), 2,2'-thiobis (4-methyl-6-tert-butylphenol), bis (3,5-di-tert-butyl-4-hydroxybenzyl) sulfide, 4,4'-di-thiobis (2, 6-di-tert-butylphenol), 4,4'-tri-thiobis (2,6-di-tert-butylphenol), 2,4-bis (n-octylthio) -6- ( 4-Hydroxy-3', 5'-di-tert-butylanilino) -1,3,5-triazine, N, N'-hexamethylenebis- (3,5-di-tert-butyl-4-hydroxyhydrocinna) Mido), N, N'-bis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionyl] hydrazine, 1,1,3-tris (2-methyl-4-hydroxy-5-) tert-butylphenyl) butane, 1,3,5-trimethyl-2,4,6-tris (3,5-di-tert-butyl-4-hydroxybenzyl) benzene, tris (3,5-di-tert- Butyl-4-hydroxyphenyl) isocyanurate, tris (3,5-di-tert-butyl-4-hydroxybenzyl) isocyanurate, 1,3,5-tris (4-tert-butyl-3-hydroxy-2, 6-Dimethylbenzyl) isocyanurate, 1,3,5-tris2 [3 (3,5-di-tert-butyl-4-hydroxyphenyl) propionyloxy] ethyl isocyanurate, tetrakis [methylene-3- (3') , 5'-di-tert-butyl-4-hydroxyphenyl) propionate] methane and the like. These can be preferably used.

More preferably, n-octadecyl-β- (4'-hydroxy-3', 5'-di-tert-butylfell) propionate, 2-tert-butyl-6- (3'-tert-butyl-5'-methyl -2'-Hydroxybenzyl) -4-methylphenyl acrylate, 3,9-bis {2- [3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy] -1,1,- Dimethylethyl} -2,4,8,10-tetraoxaspiro [5,5] undecane, and tetrakis [methyl-3- (3', 5'-di-tert-butyl-4-hydroxyphenyl) propionate] methane Is. Further, n-octadecyl-β- (4'-hydroxy-3', 5'-di-tert-butylfell) propionate is preferable.
(Sulfur-containing antioxidant)
A sulfur-containing antioxidant can also be used as an antioxidant in the resin composition constituting the thermoplastic resin sheet. It is particularly suitable when the resin composition is used for rotary molding or compression molding.

Specific examples of such sulfur-containing antioxidants include dilauryl-3,3'-thiodipropionic acid ester, ditridecyl-3,3'-thiodipropionic acid ester, and dimyristyl-3,3'-thiodipropionic acid ester. , Distearyl-3,3'-thiodipropionic acid ester, laurylstearyl-3,3'-thiodipropionic acid ester, pentaerythritol tetra (β-laurylthiopropionate) ester, bis [2-methyl-4 -(3-Laurylthiopropionyloxy) -5-tert-butylphenyl] sulfide, octadecyldisulfide, mercaptobenzimidazole, 2-mercapto-6-methylbenzimidazole, 1,1'-thiobis (2-naphthol), etc. be able to. More preferably, pentaerythritol tetra (β-laurylthiopropionate) ester can be mentioned.

The phosphorus-based heat stabilizer, the phenol-based heat stabilizer, and the sulfur-containing antioxidant listed above can be used alone or in combination of two or more. The content of the phenolic heat stabilizer and the sulfur-containing antioxidant is preferably 0.0001 to 1 part by weight with respect to 100 parts by weight in total of the A component and the B component. It is more preferably 0.0005 to 0.5 parts by weight, and even more preferably 0.001 to 0.2 parts by weight.
(Release agent)
A mold release agent can be further added to the resin composition constituting the thermoplastic resin sheet for the purpose of improving the productivity at the time of molding and reducing the distortion of the molded product. As such a mold release agent, a known one can be used.

For example, saturated fatty acid esters, unsaturated fatty acid esters, polyolefin waxes (polyethylene wax, 1-alkene polymer, etc. those modified with functional group-containing compounds such as acid modification can also be used), silicone compounds, fluorine compounds ( Fluorine oil typified by polyfluoroalkyl ether), paraffin wax, beeswax and the like can be mentioned.

Among them, fatty acid ester is mentioned as a preferable mold release agent. Such fatty acid esters are esters of fatty alcohols and aliphatic carboxylic acids. The aliphatic alcohol may be a monohydric alcohol or a divalent or higher polyhydric alcohol. The carbon number of the alcohol is preferably in the range of 3 to 32, more preferably in the range of 5 to 30.

Examples of such monohydric alcohols include dodecanol, tetradecanol, hexadecanol, octadecanol, eicosanol, tetracosanol, ceryl alcohol, and toriacontanol.

Examples of such polyhydric alcohols include pentaerythritol, dipentaerythritol, tripentaerythritol, polyglycerol (triglycerol to hexaglycerol), trimethylolpropane, xylitol, sorbitol, and mannitol. In the fatty acid ester of the present invention, a polyhydric alcohol is more preferable.

On the other hand, the aliphatic carboxylic acid preferably has 3 to 32 carbon atoms, and particularly preferably an aliphatic carboxylic acid having 10 to 22 carbon atoms.

Examples of the aliphatic carboxylic acid include decanoic acid, undecanoic acid, dodecanoic acid, tridecanoic acid, tetradecanoic acid, pentadecanoic acid, hexadecanoic acid (palmitic acid), heptadecanoic acid, octadecanoic acid (stearic acid), nonadecanoic acid and bechenic acid. Saturated aliphatic carboxylic acids such as icosanoic acid and docosanoic acid, and unsaturated aliphatic carboxylic acids such as palmitoleic acid, oleic acid, linoleic acid, linolenic acid, eicosenoic acid, eicosapentaenoic acid, and setreic acid can be mentioned. .. Among the above, the aliphatic carboxylic acid preferably has 14 to 20 carbon atoms. Of these, saturated aliphatic carboxylic acids are preferable. Particularly stearic acid and palmitic acid are preferred.

The above-mentioned aliphatic carboxylic acids such as stearic acid and palmitic acid are usually produced from animal fats and oils represented by beef fat and pork fat and natural fats and oils such as vegetable fats and oils represented by palm oil and sunflower oil. Therefore, these aliphatic carboxylic acids are usually mixtures containing other carboxylic acid components having different carbon atoms. Therefore, also in the production of the fatty acid ester of the present invention, an aliphatic carboxylic acid, particularly stearic acid or palmitic acid, which is produced from such natural fats and oils and is in the form of a mixture containing other carboxylic acid components, is preferably used.

The fatty acid ester used in the present invention may be either a partial ester or a total ester (full ester). However, the partial ester is more preferably a full ester because it usually has a high hydroxyl value and easily induces decomposition of the resin at high temperatures. The acid value of the fatty acid ester of the present invention is preferably 20 or less, more preferably 4 to 20, and even more preferably 4 to 12 from the viewpoint of thermal stability. The acid value can be substantially 0. The hydroxyl value of the fatty acid ester is more preferably in the range of 0.1 to 30. Further, the iodine value is preferably 10 or less. The iodine value can be substantially 0. These characteristics can be obtained by the method specified in JIS K0070.

The content of the release agent is preferably 0.005 to 2 parts by weight, more preferably 0.01 to 1 part by weight, still more preferably 0.05 with respect to 100 parts by weight of the total of the A component and the B component. ~ 0.5 parts by weight.
(UV absorber)
The resin composition constituting the thermoplastic resin sheet of the present invention can contain an ultraviolet absorber.

In the benzophenone system, for example, 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-octoxybenzophenone, 2-hydroxy-4-benzyloxybenzophenone, 2-hydroxy-4-methoxy- 5-Sulfoxybenzophenone, 2-hydroxy-4-methoxy-5-sulfoxitrihydride benzophenone, 2,2'-dihydroxy-4-methoxybenzophenone, 2,2', 4,4'-tetrahydroxybenzophenone, 2 , 2'-Dihydroxy-4,4'-dimethoxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxy-5-sodium sulfoxybenzophenone, bis (5-benzoyl-4-hydroxy-2-methoxyphenyl) ) Methan, 2-hydroxy-4-n-dodecyloxybenzophenone, 2-hydroxy-4-methoxy-2'-carboxybenzophenone and the like are exemplified.

In the benzotriazole system, for example, 2- (2-hydroxy-5-methylphenyl) benzotriazol, 2- (2-hydroxy-5-tert-octylphenyl) benzotriazole, 2- (2-hydroxy-3, 5-Dicumylphenyl) phenylbenzotriazole, 2- (2-hydroxy-3-tert-butyl-5-methylphenyl) -5-chlorobenzotriazole, 2,2'-methylenebis [4- (1,1,3) , 3-Tetramethylbutyl) -6- (2H-benzotriazole-2-yl) phenol], 2- (2-hydroxy-3,5-di-tert-butylphenyl) benzotriazole, 2- (2- (2-) Hydroxy-3,5-di-tert-butylphenyl) -5-chlorobenzotriazole, 2- (2-hydroxy-3,5-di-tert-amylphenyl) benzotriazole, 2- (2-hydroxy-5) -Tert-octylphenyl) benzotriazole, 2- (2-hydroxy-5-tert-butylphenyl) benzotriazole, 2- (2-hydroxy-4-octoxyphenyl) benzotriazole, 2,2'- Methylenebis (4-cumyl-6-benzotriazolephenyl), 2,2'-p-phenylenebis (1,3-benzoxazine-4-one), 2- [2-hydroxy-3- (3,4,5) , 6-Tetrahydrophthalimidemethyl) -5-methylphenyl] Benzotriazole can be mentioned. In addition, a copolymer of 2- (2'-hydroxy-5-methacryloxyethylphenyl) -2H-benzotriazole and a vinyl-based monomer copolymerizable with the monomer, and 2- (2'-hydroxy-5-acrylic). Examples thereof include a polymer having a 2-hydroxyphenyl-2H-benzotriazole skeleton, such as a copolymer of loxyethylphenyl) -2H-benzotriazole and a vinyl-based monomer copolymerizable with the monomer.

In the hydroxyphenyltriazine system, for example, 2- (4,6-diphenyl-1,3,5-triazine-2-yl) -5-hexyloxyphenol, 2- (4,6-diphenyl-1,3,5) -Triazine-2-yl) -5-methyloxyphenol, 2- (4,6-diphenyl-1,3,5-triazine-2-yl) -5-ethyloxyphenol, 2- (4,6-diphenyl) Examples thereof include -1,3,5-triazine-2-yl) -5-propyloxyphenol and 2- (4,6-diphenyl-1,3,5-triazine-2-yl) -5-butyloxyphenol. Will be done. Further, the phenyl group of the above-exemplified compound such as 2- (4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine-2-yl) -5-hexyloxyphenol is 2,4-dimethyl. A compound that has become a phenyl group is exemplified.

In the cyclic iminoester system, for example, 2,2'-p-phenylene bis (3,1-benzoxazine-4-one), 2,2'-(4,4'-diphenylene) bis (3,1-benzoxazine) -4-one), 2,2'-(2,6-naphthalene) bis (3,1-benzoxazine-4-one) and the like are exemplified.

In the cyanoacrylate system, for example, 1,3-bis-[(2'-cyano-3', 3'-diphenylacryloyl) oxy] -2,2-bis [(2-cyano-3,3-diphenylacryloyl) oxy] ] Methyl) propane, 1,3-bis-[(2-cyano-3,3-diphenylacryloyl) oxy] benzene and the like are exemplified.

Further, the above-mentioned ultraviolet absorber has a structure of a monomer compound capable of radical polymerization, so that it has a photostable monomer having such an ultraviolet-absorbing monomer and / or a hindered amine structure, and an alkyl (meth) acrylate. It may be a polymer type ultraviolet absorber which is copolymerized with a monomer such as. As the ultraviolet-absorbing monomer, a compound containing a benzotriazole skeleton, a benzophenone skeleton, a triazine skeleton, a cyclic imino ester skeleton, and a cyanoacrylate skeleton in the ester substituent of the (meth) acrylic acid ester is preferably exemplified. Ru.

Among the above, benzotriazole-based and hydroxyphenyltriazine-based are preferable in terms of ultraviolet absorption ability, and cyclic iminoester-based and cyanoacrylate-based are preferable in terms of heat resistance and hue (transparency). The above-mentioned ultraviolet absorber may be used alone or in a mixture of two or more kinds.

The content of the ultraviolet absorber is preferably 0.01 to 2 parts by weight, more preferably 0.02 to 2 parts by weight, still more preferably 0.03 with respect to 100 parts by weight of the total of the A component and the B component. It is ~ 1 part by weight, more preferably 0.05 to 0.5 part by weight.
(Hinderdamine-based light stabilizer)
The resin composition constituting the thermoplastic resin sheet can contain a hindered amine-based light stabilizer. The hindered amine-based light stabilizer is generally called HALS (Hindered Amine Light Stabilizer), and is a compound having a 2,2,6,6-tetramethylpiperidine skeleton in its structure.

For example, 4-acetoxy-2,2,6,6-tetramethylpiperidine, 4-stearoyloxy-2,2,6,6-tetramethylpiperidine, 4-acryloyloxy-2,2,6,6-tetramethyl Piperidine, 4- (phenylacetoxy) -2,2,6,6-tetramethylpiperidine, 4-benzoyloxy-2,2,6,6-tetramethylpiperidine, 4-methoxy-2,2,6,6- Tetramethylpiperidine, 4-stearyloxy-2,2,6,6-tetramethylpiperidine, 4-cyclohexyloxy-2,2,6,6-tetramethylpiperidine, 4-benzyloxy-2,2,6,6 -Tetramethylpiperidine, 4-phenoxy-2,2,6,6-tetramethylpiperidine, 4- (ethylcarbamoyloxy) -2,2,6,6-tetramethylpiperidine, 4- (cyclohexylcarbamoyloxy) -2 , 2,6,6-tetramethylpiperidine, 4- (phenylcarbamoyloxy) -2,2,6,6-tetramethylpiperidine, bis (2,2,6,6-tetramethyl-4-piperidyl) carbonate, Bis (2,2,6,6-tetramethyl-4-piperidyl) oxalate, bis (2,2,6,6-tetramethyl-4-piperidyl) malonate, bis (2,2,6,6-tetramethyl) -4-piperidyl) sebacate, bis (2,2,6,6-tetramethyl-4-piperidyl) adipate, bis (2,2,6,6-tetramethyl-4-piperidyl) terephthalate, bis (1,2) , 2,6,6-pentamethyl-4-piperidyl) carbonate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) oxalate, bis (1,2,2,6,6-pentamethyl-4) -Piperidyl) malonate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) adipate, bis (1,2) , 2,6,6-pentamethyl-4-piperidyl) terephthalate, N, N'-bis-2,2,6,6-tetramethyl-4-piperidinyl-1,3-benzenedicarboxyamide, 1,2- Bis (2,2,6,6-tetramethyl-4-piperidyloxy) ethane, α, α'-bis (2,2,6,6-tetramethyl-4-piperidyloxy) -p-xylene, bis (2,2,6,6-tetramethyl-4-piperidyloxy) 2,2,6,6-Tetramethyl-4-piperidyltrilen-2,4-dicarbamée To, bis (2,2,6,6-tetramethyl-4-piperidyl) -hexamethylene-1,6-dicarbamate, tris (2,2,6,6-tetramethyl-4-piperidyl) -benzene- 1,3,5-tricarboxylate, N, N', N'', N'''-tetrakis- (4,6-bis- (butyl- (N-methyl-2,2,6,6-tetra) Methylpiperidin-4-yl) amino) -triazine-2-yl) -4,7-diazadecan-1,10-diamine, dibutylamine 1,3,5-triazine N, N'-bis (2,2) , 6,6-Tetramethyl-4-piperidyl) -1,6-hexamethylenediamine and N- (2,2,6,6-tetramethyl-4-piperidyl) butylamine polycondensate, poly [{6 -(1,1,3,3-tetramethylbutyl) amino-1,3,5-triazine-2,4-diyl} {(2,2,6,6-tetramethyl-4-piperidyl) imino} hexa Methylene {(2,2,6,6-tetramethyl-4-piperidyl) imino}], tetrakis (2,2,6,6-tetramethyl-4-piperidyl) -1,2,3,4-butanetetra Carboxylate, tetrakis (1,2,2,6,6-pentamethyl-4-piperidyl) -1,2,3,4-butane tetracarboxylate, tris (2,2,6,6-tetramethyl-4- Piperidil) -benzene-1,3,4-tricarboxylate, 1- [2- {3- (3,5-di-t-butyl-4-hydroxyphenyl) propionyloxy} butyl] -4- [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionyloxy] 2,2,6,6-tetramethylpiperidine, and 1,2,3,4-butanetetracarboxylic acid and 1,2,2 , 6,6-Pentamethyl-4-piperidinol and β, β, β', β'-tetramethyl-3,9- [2,4,8,10-tetraoxaspiro (5,5) undecane] diethanol Examples thereof include condensates.

Hindered amine-based photostabilizers are roughly classified according to the binding partner of the nitrogen atom in the piperidine skeleton, and are classified into NH type (hydrogen is bonded to the nitrogen atom) and NR type (alkyl group (R) is bonded to the nitrogen atom). , N-OR type (an alkoxy group (OR) is bonded to a nitrogen atom). When applied to a polycarbonate resin, it is more preferable to use the low-basic NR type and N-OR type from the viewpoint of the basicity of the hindered amine-based light stabilizer. The above-mentioned hindered amine-based light stabilizer can be used alone or in combination of two or more.

The content of the hindered amine-based light stabilizer is preferably 0 to 1 part by weight, more preferably 0.05 to 1 part by weight, still more preferably 0, based on 100 parts by weight of the total of the A component and the B component. It is .08 to 0.7 parts by weight, particularly preferably 0.1 to 0.5 parts by weight. If the content of the hindered amine-based light stabilizer is more than 1 part by weight, the appearance may be poor due to gas generation and the physical properties may be deteriorated due to the decomposition of the polycarbonate resin, which is not preferable. Further, if it is less than 0.05 parts by weight, sufficient light resistance may not be exhibited.
(Flame retardants)
A flame retardant can be added to the resin composition constituting the thermoplastic resin sheet to impart flame retardancy. As the flame retardant, various compounds conventionally known as flame retardants of thermoplastic resins can be applied, but more preferably, (i) halogen-based flame retardant (for example, brominated polycarbonate compound) (ii) phosphorus-based. Flame retardants (eg, monophosphate compounds, phosphate oligomer compounds, phosphonate oligomer compounds, phosphonitrile oligomer compounds, phosphonic acid amide compounds, and phosphate compounds, etc.), (iii) Metal salt-based flame retardants (eg, organic sulfonic acid alkali (earth)). It is a silicone-based flame retardant composed of (iv) a silicone compound, such as a metal salt, a borate metal salt-based flame retardant, and a tin acid metal salt-based flame retardant. The compounding of the compound used as the flame retardant not only improves the flame retardancy but also improves the antistatic property, the fluidity, the rigidity, and the thermal stability based on the properties of each compound.

The content of the flame retardant is preferably 0.01 to 30 parts by weight, more preferably 0.05 to 28 parts by weight, still more preferably 0.08 with respect to 100 parts by weight of the total of the A component and the B component. ~ 25 parts by weight. If the content of the flame retardant is less than 0.01 parts by weight, sufficient flame retardancy may not be obtained, and if it exceeds 30 parts by weight, the impact strength and chemical resistance may be significantly reduced.
(Dyeing pigment)
It is possible to provide a molded product that further contains various dyes and pigments in the resin composition constituting the thermoplastic resin sheet and exhibits various design properties. By blending a fluorescent whitening agent or a fluorescent dye that emits light other than that, a better design effect that makes the best use of the emitted color can be imparted. It is also possible to provide a fiber-reinforced resin composition which is colored with a very small amount of dye and has a vivid color-developing property.

Examples of fluorescent dyes (including fluorescent whitening agents) include coumarin-based fluorescent dyes, benzopyran-based fluorescent dyes, perylene-based fluorescent dyes, anthracinone-based fluorescent dyes, thioindigo-based fluorescent dyes, xanthene-based fluorescent dyes, and xantone-based fluorescent dyes. , Thioxanthene-based fluorescent dyes, thioxanthone-based fluorescent dyes, thiazine-based fluorescent dyes, diaminostilben-based fluorescent dyes, and the like. Among these, coumarin-based fluorescent dyes, benzopyran-based fluorescent dyes, and perylene-based fluorescent dyes, which have good heat resistance and little deterioration during molding of the polycarbonate resin, are suitable.

Examples of dyes other than the above brewing agents and fluorescent dyes include perylene dyes, coumarin dyes, thioindigo dyes, anthracinone dyes, thioxanthone dyes, ferrocyanides such as navy blue, perinone dyes, quinoline dyes, and quinacridones. Examples thereof include dyes, dioxazine dyes, isoindrinone dyes, and phthalocyanine dyes. Further, the resin composition of the present invention can also be blended with a metallic pigment to obtain a better metallic color. As the metallic pigment, those having a metal film or a metal oxide film on various plate-shaped fillers are suitable.

The content of the dyeing pigment is preferably 0.00001 to 1 part by weight, more preferably 0.00005 to 0.5 part by weight, based on 100 parts by weight of the total of the A component and the B component.
(Other resins)
In the polypropylene resin composition constituting the thermoplastic resin sheet, other resins can be used in a small proportion as long as the effects of the present invention are exhibited.

Examples of such other resins include polyester resins such as polyethylene terephthalate and polybutylene terephthalate, polyamide resins, polyimide resins, polyetherimide resins, polyurethane resins, silicone resins, polyphenylene ether resins, polyphenylene sulfide resins, polysulfone resins, and polypropylene resins. Examples thereof include resins such as polyolefin resins, polymethacrylate resins, phenol resins, and epoxy resins.
(Other fillers)
In the resin composition constituting the thermoplastic resin sheet, a small proportion of other fillers can be used as long as the effect of the present invention is exhibited.

Other fillers include fibrous fillers such as potassium titanate whisker, zinc oxide whisker, alumina fiber, silicon carbide fiber, ceramic fiber, asbestos fiber, stone wool fiber, metal fiber, warastonite, sericite, kaolin. , Mica, clay, bentonite, asbestos, talc, alumina silicate and other silicates. In addition, swellable layered silicates such as montmorillonite and synthetic mica, metal compounds such as alumina, silicon oxide, magnesium oxide, zirconium oxide, titanium oxide and iron oxide, carbonates such as calcium carbonate, magnesium carbonate and dolomite, and calcium sulfate. , Sulfates such as barium sulfate, glass beads, ceramic beads, boron nitride, silicon carbide, calcium phosphate and non-fibrous fillers such as silica.
(Other additives)
In the resin composition constituting the thermoplastic resin sheet of the present invention, an additive known per se can be blended in a small proportion in order to impart various functions to the molded product and improve the characteristics. These additives are in the usual blending amount as long as the object of the present invention is not impaired. Such additives include sliding agents (eg, PTFE particles), fluorescent dyes, inorganic phosphors (eg, phosphors having aluminate as the parent crystal), antistatic agents, crystal nucleating agents, inorganic and organic antibacterial agents. , Photocatalytic antifouling agents (for example, fine particle titanium oxide, fine particle zinc oxide), radical generators, infrared absorbers (heat ray absorbers), photochromic agents and the like.
(Manufacturing method of resin composition)
The method for producing the resin composition constituting the thermoplastic resin sheet is not particularly limited, and a well-known method can be used. For example, a method of mixing each component in a solution state and evaporating the solvent or precipitating in the solvent can be mentioned. From an industrial point of view, a method of kneading each component in a molten state is preferable. For melt kneading, a commonly used single-screw or twin-screw extruder, various kneaders, and other kneading devices can be used. In particular, a biaxial high kneader is preferable. In melt kneading, the cylinder set temperature of the kneading device is preferably in the range of 200 to 360 ° C, more preferably in the range of 200 ° C to 300 ° C, and further preferably in the range of 230 to 280 ° C. In kneading, each component may be mixed uniformly in advance with a device such as a tumbler or a Henschel mixer, or if necessary, mixing may be omitted and a method of separately quantitatively supplying each component to the kneading device is also used. be able to.
(Thermoplastic resin sheet)
The thermoplastic resin sheet used in the present invention is formed by stacking reinforcing fiber sheets at a temperature equal to or higher than the melting temperature of the thermoplastic resin constituting the thermoplastic resin sheet and lower than the heat resistant temperature of the reinforcing fibers constituting the reinforcing fiber sheet. By the pressure treatment, the thermoplastic resin sheet is melted and arranged without voids around the reinforcing fibers to form a fiber-reinforced resin composite.

The form of the thermoplastic resin sheet used in the present invention is not particularly limited, but at least one of the three dimensions of length, width, and thickness is in the range of 1 to 300 μm in order to achieve the above object. It is preferable, 1 to 100 μm is more preferable, 1 to 50 μm is even more preferable, and 1 to 30 μm is most preferable. Examples of those having such a form include films, non-woven fabrics, and the mesh-like fiber sheets listed below, and among them, the mesh-like fiber sheet is preferable from the viewpoint of impregnation of the reinforcing fiber of the thermoplastic resin sheet into the periphery.
(Reticulated fiber sheet)
In the present invention, by using the thermoplastic resin sheet as a mesh-like fiber sheet, higher adhesion to the reinforcing fibers can be obtained as compared with a normal non-woven fabric made of fibers having no mesh structure. Further, in order to obtain high adhesion to the reinforcing fiber, it is preferable that the hollow fiber is a deformed fiber having an irregular cross-sectional shape. Here, the term “hollow” is not limited to those having obvious voids such as known hollow fibers, but may be those having bubbles inside the fibers.

The hollow fiber described in the present invention has air bubbles inside the fiber. For example, as schematically shown in FIG. 1, the hollow fiber has non-continuous air bubbles inside and has an irregular non-circular cross section. It is preferably a thing.

More specifically, as shown in the electron micrograph of FIG. 2, it is preferable that it is a flat fibrous material having a plurality of bubbles having different shapes inside.

Here, the bubbles inside the deformed fiber refer to the closed space (void) existing inside the fiber. Usually, the voids inside the synthetic fiber are voids having the same cross-sectional shape continuous in the fiber axis direction, as seen in hollow fibers and the like. Unlike this, the preferred voids of the present invention are in the form of discontinuous air bubbles. In the present invention, it is preferable to have such discontinuous bubbles having different cross-sectional shapes in the length direction of the fiber inside the hollow fiber. When a non-continuous bubble-like void, which is a preferable shape of the present invention, is present, it is possible to uniformly improve the fluidity of the thermoplastic resin, unlike the case of a normal continuous void. As a result, it is possible to exhibit particularly excellent impregnation property in the composite with the reinforcing fiber as compared with the continuous voids.

The thermoplastic resin fiber used in the present invention has bubbles inside the fiber as described above, but the hollow ratio in the cross section of the single fiber is preferably in the range of 0.5 to 40%. Here, the hollow ratio means the ratio of the total area of the bubbles in the fiber cross section when a plurality of bubbles are included in the fiber cross section. Further, the hollow ratio of the fiber is preferably in the range of 1 to 30%, particularly preferably 5 to 20%. If the hollow ratio of the fiber is less than 0.5%, the impregnation property at the time of compounding with the reinforcing fiber may be insufficient, and if it exceeds 40%, the strength of the non-woven fabric structure is lowered. In addition, in the fiber manufacturing process such as spinning, especially in the case of irregularly shaped fibers, many fiber breaks occur and the manufacturing efficiency tends to decrease.

This hollow ratio is obtained by determining the area of the hollow portion with respect to the total cross-sectional area including the hollow portion of the fiber as the hollow ratio from the fiber cross-sectional photograph of the image obtained at a magnification of 100 times with a scanning electron microscope (SEM). be. In the present invention, the presence of such a hollow portion makes the wall portion of the fiber cross section thin and easily dissolves, and the moldability for a particularly fine portion is improved. However, if the hollow ratio of the fiber is too large, the thermal conductivity of the entire hollow fiber becomes small, and the molding efficiency tends to decrease.

The size of each bubble is preferably in the range of 0.1 to 100 μm. In particular, it is preferably in the range of 0.5 to 50 μm. If the size of the bubbles is smaller than 0.1 μm, the impregnation property at the time of compounding with the reinforcing fiber may be insufficient, and if it is larger than 100 μm, the compounding with the reinforcing fiber does not occur uniformly. Instead, defects (air bubbles) may remain inside the reinforced fiber plastic.

In the present invention, a deformed fiber is preferably used, but the irregular non-circular cross section in the outer peripheral cross section of the deformed fiber is a shape in which the cross section shape is more disordered than a regular cross section such as an ellipse or a regular polygon. Is preferable. Since the cross-sectional shape of a normal synthetic fiber depends on the shape of the spinneret, it is generally a regular cross-section. This is because an irregular base shape increases the rate of yarn breakage during melt spinning. However, when the irregular shape of the cross section is regular, when the nonwoven fabric is formed, another fiber may be contained in the irregular shape portion of the fiber and packed tightly, and the voids may be reduced. The mesh-like fiber of the present invention is different from the above, and is preferably a fiber having a cross-sectional shape that does not depend on the shape of the base. The fibers constituting the thermoplastic resin sheet of the present invention are preferably deformed fibers obtained by slit spinning using a foaming agent, as will be described later, for example.

And by having such an irregular outer cross section and a mesh-like morphology, not only voids are always generated in the overlapping portion of each irregularly shaped fiber, but also interfiber voids take various shapes. The voids between the fibers are not uniform, and the overlap of fibers is reduced. In addition, the irregular shape makes the bending rigidity and the density of the substance random. And, by being random in this way, it is possible to have uniform mechanical properties as a result in the composite with the reinforcing fiber.

The end face angle of the hollow fiber used in the present invention is preferably less than 60 degrees, more preferably 1 to 55 degrees, and even more preferably 3 to 45 degrees. This end face angle is obtained from the fiber cross-section photograph of the image obtained at a magnification of 100 times with a scanning electron microscope (SEM) as in the above-mentioned measurement of the hollow ratio, and is a straight line (length) connecting both ends of the fiber cross section. A straight line (short axis) is defined at the thickest part in the direction orthogonal to the axis), and the long axis of the triangle connecting both ends of the short axis and the end of the long axis near the short axis. The angle of the end was calculated and used as the end face angle. When the end face angle is less than 60 degrees, hollow fibers made of a thermoplastic resin easily penetrate between the reinforcing fibers, and it may be possible to secure higher impregnation property.

As the deformed fiber preferably used in the present invention, it is preferable that the degree of deformation is larger than 1 and 20 or less in the cross section of the single fiber. Further, the degree of deformation is preferably 2 to 10. Here, the degree of deformation of the cross-sectional shape of the fiber is a numerical value defined by the ratio D1 / D2 of the circumscribed circle diameter D1 and the inscribed circle diameter D2 of the cross section of the single fiber shown in FIG. When the degree of atypia is in the above preferable range, excellent impregnation property can be exhibited at the time of compounding with the reinforcing fiber. More specifically, this degree of atypia is obtained from the fiber cross-sectional photograph of the image obtained at a magnification of 100 times with a scanning electron microscope (SEM) as in the measurement of the hollowness ratio and the like, and is obtained in the transverse cross section. The diameter D1 of the extrinsic circle and the diameter D2 of the inscribed circle are measured, and the ratio (D1 / D2) is calculated as the degree of atypia. Contrary to the end face angle, when the value of this atypia is large, hollow fibers made of a thermoplastic resin easily penetrate between the reinforcing fibers, and it becomes possible to secure higher impregnation property.

In the method for producing a mesh fiber sheet of the present invention, first, in order to obtain a deformed fiber, a thermoplastic resin to which a foaming agent is added is extruded from a slit die and molded. At this time, the thermoplastic resin discharged from the slit die becomes a thin sheet, but since the foaming agent is added to the thermoplastic resin used in the present invention, the resin is discharged from the slit die. A mesh-like sheet is formed by foaming inside and allowing air bubbles to pass to the outside of the thin sheet. At the same time, each fiber constituting the mesh-like sheet becomes a deformed fiber. On the contrary, the bubbles staying inside the resin without going out form voids inside the deformed fiber. FIG. 1 is a schematic diagram thereof. The electron micrograph of FIG. 2 is a cross-sectional photograph of an aggregate of deformed fibers produced by such a step of the present invention. As described above, in the present invention, the thermoplastic resin contains a foaming agent, but the foaming agent is a foamable substance and may be a substance that becomes a gas when the molten resin is extruded from the slit die. It's fine. This foaming agent is not necessarily a substance that foams by itself, and the resin itself may also serve as a foaming agent having the property of generating such a gas, or may be a substance that helps to generate a gas. .. Specific methods for obtaining a mesh fiber sheet include, for example, a method of kneading a substance such as an inert gas that is a gas at room temperature such as nitrogen gas and carbon dioxide gas into a molten thermoplastic resin, and a method of kneading a substance such as water at room temperature. However, a method of kneading a substance that becomes a gas at the melting temperature of the thermoplastic resin with the molten thermoplastic resin, for example, a method of kneading a substance that generates a gas by decomposition such as a diazo compound or sodium carbonate with the molten thermoplastic resin. For example, a method of kneading a polymer that reacts with a part of a molten thermoplastic resin such as polycarbonate (for example, polyester or polyamide) to generate a gas with such a molten thermoplastic resin can be adopted.

In any method, when the thermoplastic resin is extruded from the slit die in a molten state, gas may be generated from the die together with the resin, and the various foamable substances and the thermoplastic resin described above are the slit die. It is preferably well kneaded before being extruded from. If this kneading is not sufficient, it may be difficult to obtain a mesh-like fiber sheet or deformed fiber having uniform and desired physical properties.

At the same time, in the production method of the present invention, it is preferable to generate bubbles inside the fiber. The foaming agent for this purpose is particularly suitable to be an inert gas. When an inert gas is used, the inert gas dissolves in the thermoplastic resin in a small amount under the conditions of high temperature and high pressure during melt spinning. Then, when the gas is extruded from the slit die, a large number of minute bubbles are generated, especially when the inert gas is used. In the present invention, discontinuous bubbles can be stably generated inside the deformed fiber by the generation of bubbles during the spinning process and further by the elution of the dissolved inert gas. ..

It is preferable that the resin discharged from the die is cooled quickly. This cooling is also a factor that determines the size of the mesh at the mesh fiber sheet stage and the fiber diameter and shape of the finally obtained deformed fiber, so it is desirable to manage it sufficiently. For example, when it is desired to produce a mesh-like fiber sheet having a large fiber diameter and a large mesh, cooling may be reduced. If the fiber diameter is small and the mesh is thin, the reverse is recommended. Generally, the air cooling method is preferable for this cooling, and the mesh and fiber diameter are adjusted by changing the air volume, but a liquid such as water or contact with a cooled solid is used. Is also possible.

Further, as a method for producing this mesh-like fiber sheet, it is preferable that the thermoplastic resin is extruded from the slit die together with the foaming agent in a molten state, and then the discharged resin is taken up at a sufficient speed. If the take-up speed is not sufficient, the strength of the mesh-like fiber sheet or the deformed fiber obtained may be weakened, or in an extreme case, a large hole may be formed in the sheet, and a uniform deformed fiber may not be obtained. The guideline for the pick-up speed is expressed by the draft rate, and is usually 10 times or more, preferably 20 to 400 times. Further, it is preferable that the draft rate is 300 times or less, particularly 20 to 200 times. Here, if the draft rate is too low, the fibers tend to be too thick. On the contrary, if it is too high, yarn breakage will occur, and it tends to be difficult to manufacture a stable mesh fiber sheet. Here, the draft is to stretch the fibers to orient the molecules of the resin and improve the strength. The draft rate used here is expressed by the ratio of the take-up speed to the linear speed of the resin passing through the die. When the extension described later is performed during the collection, the speed is converted to the speed when the extension is not performed and used as the draft rate.

Further, one method of adjusting the mesh size of the mesh-like fiber sheet used in the present invention and the fiber diameter of the deformed fiber is to change the melt viscosity of the resin. As a method of changing the melt viscosity, for example, there are a method of changing the temperature condition, a method of changing the degree of polymerization of the resin, a method of using a plasticizer, or a method of using a combination thereof, but the method of changing the temperature condition is the most important. Easy and preferable. Further, the degree of deformation, the hollow ratio, and the shape of the hollow voids of the above-mentioned deformed fibers can be adjusted by adjusting the amount of the foamable substance added in spinning, the temperature condition, the draft rate, and the like.

It is preferable that the deformed fiber of the present invention undergoes the state of the mesh-like fiber sheet as described above in the middle of its production. By passing through the form of a mesh-like fiber sheet, it is possible to easily draft and spread at a large magnification, and stable productivity can be ensured. As a result, deformed fibers having sufficient strength can be easily obtained. In the present invention, it is preferable that the deformed fibers in the nonwoven fabric structure contain bubbles inside and the cross-sectional shape thereof is irregular and non-circular. However, such deformed fibers usually have low strength, and it is very difficult to produce them in an industrially stable manner. However, once the fiber sheet is formed as a mesh as described above, high-strength deformed fibers with less yarn breakage can be stably produced.

Further, such a mesh-like fiber sheet can be further made into a uniform and high-strength mesh-like fiber sheet by the spreading step described below, and has excellent impregnation property into the reinforcing fiber sheet. High physical characteristics can be obtained for the body. Here, the spreading step means a step of stretching the mesh-like fiber sheet in the horizontal direction to expand the mesh. Specific methods include, for example, a method of expanding the mesh fiber sheet in the horizontal direction while grasping both ends thereof, and a method of expanding the mesh fiber sheet extruded from the circular slit in the diameter direction of the slit. .. In particular, a method of stacking a large number of sheets and expanding them in the horizontal direction while grasping both ends thereof is preferable. Not only is the industrial productivity higher than other methods, but the lamination improves the uniformity in the thickness direction and the width direction. As described above, the method of expanding in the horizontal direction may be any method such as a method of grasping and expanding only both ends, a method of dividing into several zones in the width direction and expanding each zone, and other methods. When the above-mentioned spreading is performed, it may be carried out as it is on one mesh fiber sheet, or two or more sheets may be laminated. When two or more sheets are laminated, the number of sheets is preferably 2 to 2000, preferably 10 to 1000. The mesh-like fiber sheets to be laminated may be of the same type, or a plurality of mesh-like fiber sheets made of different polymers may be laminated together. Further, it is also possible to combine a non-woven fabric web made of short fibers, a long-fiber non-woven fabric such as a spunbonded non-woven fabric, and the like.
(Reinforcing fiber sheet)
The reinforcing fiber constituting the reinforcing fiber sheet used in the laminate of the present invention is preferably a reinforcing fiber having a heat resistance of 350 ° C. or higher.

Specifically, inorganic fibers such as high-strength carbon fibers, glass fibers, and metal fibers, and organic synthetic fibers such as aromatic polyamide fibers can be used. Further, these may be used alone or in combination of two or more. Examples of the metal fiber include stainless steel fiber, which is preferable in terms of conductivity and mechanical properties. Further, the surface of the reinforcing fiber may be coated with a metal or the like or vapor-filmed. For example, nickel-coated carbon fiber is preferred in terms of conductivity. In particular, carbon fibers and glass fibers having high strength and high elasticity are preferable, and carbon fibers, more specifically polyacrylonitrile (PAN) type, petroleum / coal pitch type, are used to obtain a highly rigid laminate. , Rayon-based, lignin-based and other carbon fibers can be mentioned. In particular, PAN-based carbon fiber made from PAN is preferable because it is excellent in productivity and mechanical properties on an industrial scale.

Further, the reinforcing fiber used in the present invention may have a fiber shape long in one direction, and is a concept including not only general fibers and filaments but also so-called whiskers and the like.

More specifically, examples of reinforcing fibers preferably used in the present invention are glass fibers, flat cross-section glass fibers, carbon fibers, metal fibers, asbestos, rock wool, ceramic fibers, slag fibers, potassium titanate whisker, and boron whisker. , Aluminum borate whisker, Calcium carbonate whisker, Titanium oxide whisker, Wallastnite, Zonotolite, Parigorskite (atapaljite), and fibrous material consisting of inorganic fillers such as sepiolite, aramid fiber, polyimide fiber, PBO (polyparaphenylene benz) Examples thereof include heat-resistant organic fibers typified by heat-resistant organic fibers such as oxazole) fibers and polybenzthiazole fibers, and fibers in which a different material such as a metal or a metal oxide is surface-coated on these fibers.

As the fiber surface-coated with different materials, a fibrous form is sufficient, and examples thereof include metal-coated glass fiber, metal-coated glass flake, titanium oxide-coated glass flake, and metal-coated carbon fiber. The method of surface coating of different materials is not particularly limited, and for example, various known plating methods (for example, electrolytic plating, electroless plating, hot-dip plating, etc.), vacuum vapor deposition method, ion plating method, CVD method (for example). For example, thermal CVD, MOCVD, plasma CVD, etc.), PVD method, sputtering method and the like can be mentioned.

Among these reinforcing fibers, one selected from glass fiber, carbon fiber and aramid fiber is preferable, and at least one selected from carbon fiber and glass fiber is more preferable. Further, as these reinforcing fibers for reinforcement, only one kind may be used, or a plurality of kinds may be used.

As the thickness of the reinforcing fiber, so-called fineness, it is preferable to use one having an average diameter of 3 to 20 μm, and further preferably 5 to 15 μm. In such a range, not only the physical characteristics of the fiber are high, but also the dispersibility in the thermoplastic resin that finally becomes the matrix is excellent. Further, from the viewpoint of productivity, it is also preferable that the reinforcing fiber is a fiber bundle of 1,000 to 50,000 single fibers.

Further, the reinforcing fiber used in the laminate of the present invention preferably has a high strength in order to finally reinforce the resin, and the tensile strength of the fiber is 3500 MPa to 7000 MPa, and the modulus is It is preferably 220 GPa to 900 GPa. From the viewpoint of finally obtaining a high-strength molded product, carbon fiber is particularly preferable as the reinforcing fiber, and PAN-based carbon fiber is more preferable.

The surface of the carbon fiber is preferably oxidized for the purpose of increasing the compatibility with the matrix resin and improving the dispersibility of the polypropylene resin and the polycarbonate resin. Although the mechanism is not yet clear, by oxidizing the surface of the carbon fiber, the polarity of the surface is improved, and the adhesion between the non-polar propylene resin and the carbon fiber is further lowered. As a result, it is considered that the adhesion to the polycarbonate resin having a relatively high polarity is improved.

The degree of oxidation treatment can be quantified by the surface oxygen concentration (O / C) on the carbon fiber. The surface oxygen concentration (O / C) on the carbon fiber is the surface oxygen concentration (O / C) which is the ratio of the number of atoms of oxygen (O) and carbon (C) on the fiber surface measured by X-ray photoelectron spectroscopy. ) Is preferably 0.15 or more, more preferably 0.18 or more, and further preferably 0.2 or more. If the surface oxygen concentration is less than 0.15, the adhesion between the carbon fiber and the polycarbonate resin may be insufficient, which is not preferable. The upper limit of the surface oxygen concentration is not particularly limited, but is generally preferably 0.5 or less from the viewpoint of the balance between the handleability and productivity of carbon fibers.

The oxidation treatment method is not particularly limited, and for example, (1) a method of treating carbon fibers with an acid or an alkali or a salt thereof, or an oxidizing gas, and (2) a carbon fiberizable fiber or a fibrous carbon filler. , A method of firing at a temperature of 700 ° C. or higher in the presence of an inert gas containing an oxygen-containing compound, and (3) a method of oxidizing carbon fibers and then heat-treating in the presence of an inert gas are preferably exemplified. Will be done.

As the existing form of these reinforcing fibers in the laminate, either long fiber or short fiber can be used. However, from the viewpoint of reinforcing the resin, it is preferable to have a long fiber shape, and conversely, from the viewpoint of making the physical properties of the obtained complex isotropic, it is preferable to have a structure mainly composed of short fibers. Here, the short fiber means a discontinuous fiber that is not a long fiber. When used as short fibers, it is preferable that the reinforcing fiber sheet is a fiber aggregate or a non-woven fabric in which the orientation of the fibers is randomized in advance.

When the reinforcing fiber is used as a short fiber (discontinuous fiber), its length is preferably 300 μm or more, more preferably 3 mm or more, further preferably 6 mm or more, and further preferably 20 mm. The above is the most preferable. When used as a staple fiber, it is preferably 100 mm or less, more preferably 80 mm or less, and particularly preferably 60 mm or less. When such a fiber is used as a non-woven fabric shape, anisotropy with respect to strength and dimensions is improved.

On the other hand, when the reinforcing fiber is used as a long fiber, it can be used in various forms such as a unidirectional sheet, a woven fabric, a knitted fabric, and a braid. However, from the viewpoint of reinforcing the strength of the finally obtained complex, it is preferable to use it as a unidirectional sheet (so-called UD sheet). Alternatively, it is preferable that part or all of the reinforcing fibers are unidirectional fiber sheets or unidirectional tapes, and these are partially used. As a particularly preferable form when used as a long fiber, a woven fabric having two or three axes is also preferable. Further, as these fiber forms, it is also possible to partially use one kind or a combination of two or more kinds of forms.

The content of the reinforcing fiber constituting the reinforcing fiber sheet used in the present invention is 151 to 900 parts by weight, preferably 300 to 800 parts by weight, based on 100 parts by weight of the total of the A component and the B component. It is more preferably 400 to 700 parts by weight, still more preferably 550 to 650 parts by weight. If the content of the reinforcing fibers is less than 151 parts by weight, the strength of the fiber-reinforced resin composite is not sufficiently exhibited, and if it exceeds 900 parts by weight, many slips of the reinforcing fibers occur and the strength becomes non-uniform.
(Laminating method)
Further, in the laminate of the present invention, the above-mentioned thermoplastic resin sheet and the reinforcing fiber sheet are superposed, and the temperature is equal to or higher than the melting temperature of the thermoplastic resin constituting the thermoplastic resin sheet, and the reinforcing fiber sheet is formed. A fiber-reinforced resin composite can be obtained by pressure-treating at a temperature lower than the heat-resistant temperature of the fiber.

The weight ratio of the thermoplastic resin sheet to the reinforcing fiber sheet is preferably in the range of 45:55 to 20:80, and more preferably in the range of 35:65 to 25:75. As the thermoplastic resin sheet, the thickness is preferably 0.05 to 0.5 mm when the thickness is measured under the condition of a load of 1.25 N / cm ² using a peacock with a stylus having a diameter of 8 mm. , 0.1 to 0.3 mm is more preferable, and the texture is preferably in the range of 2 to 100 g / m ² . The reinforcing fiber sheet preferably has a thickness of 0.05 to 1.0 mm and a basis weight of 100 to 2000 g / m ² .

The laminate of the present invention is a stack of a plurality of such thin thermoplastic resin sheets and reinforcing fiber sheets, and the stacking method is that they are alternately arranged. It is preferable to arrange a thermoplastic resin sheet on the surface. The number of reinforcing fiber sheets is preferably 1 to 5, more preferably 1 to 3, and even more preferably 1 to 2. FIG. 4 shows a schematic cross-sectional view of the laminated body of the present invention. In FIG. 4, reference numeral 5 is a thermoplastic resin sheet layer, and reference numeral 6 is a reinforcing fiber sheet layer.
<Fiber reinforced plastic complex>
The fiber-reinforced resin composite of the present invention comprises the above-mentioned laminate of the present invention. The fiber-reinforced resin composite of the present invention is obtained by pressure-treating a laminated body, and has a structure in which reinforcing fiber sheets are laminated via a thermoplastic resin sheet. A part of the thermoplastic resin sheet of the laminated body is impregnated with the reinforcing fiber sheet, but basically has the same cross-sectional shape as the laminated body. FIG. 5 shows a schematic cross-sectional view of the fiber reinforced resin complex of the present invention. In FIG. 5, reference numeral 5 is a thermoplastic resin sheet layer, and reference numeral 6 is a reinforcing fiber sheet layer.
<Manufacturing method of fiber reinforced resin composite>
The fiber-reinforced resin complex of the present invention can be obtained by pressure-treating the laminate of the present invention. Specifically, the above-mentioned laminate is pressure-treated at a temperature equal to or higher than the melting temperature of the thermoplastic resin constituting the thermoplastic resin sheet and lower than the heat resistant temperature of the reinforcing fiber constituting the reinforcing fiber sheet. Can be manufactured.

By this method, the reinforcing fiber is surrounded by the thermoplastic resin, but it is preferable that there are no voids in order to improve the physical properties of the complex. The temperature of the pressurizing treatment depends on the thermoplastic resin used, but is preferably in the range of 200 to 340 ° C., more preferably 240 to 330 ° C. The treatment time is preferably about 1 to 30 minutes, more preferably about 1 to 10 minutes, and particularly preferably in the range of 3 to 10 minutes. The press pressure during processing is preferably in the range of 2 to 30 MPa, more preferably 5 to 20 MPa.

The embodiment of the present invention, which the present inventors consider to be the best at present, is a collection of preferable ranges of the above-mentioned requirements. For example, a representative example thereof will be described in the following examples. Of course, the present invention is not limited to these forms.

Next, examples and comparative examples of the present invention will be described in detail, but the present invention is not limited thereto. In addition, each measurement item in an Example was measured by the following method.
(I) Evaluation of thermoplastic resin sheet (I-1) Metsuke (in the case of fibrous sheet)
It was measured according to JIS L 1913.
(I-2) Degree of atypia (in the case of fibrous sheet)
The ratio (D1 / D2) of the circumscribed circle diameter D1 and the inscribed circle diameter D2 of the cross section of the single fiber shown in FIG. 3 was calculated and used as the degree of atypia. The degree of deformation was expressed by the average value of the degree of deformation for 20 fibers.
(I-3) Hollow ratio (in the case of fibrous sheet)
Using an image analysis system, Pierce-2 (manufactured by Pierce Co., Ltd.), the cross-sectional area of the fiber (including the hollow portion) and the area of the hollow portion are measured from the digitized cross-sectional photograph of the fiber, and the hollow ratio (hollow ratio) is measured from the area ratio. %) Was calculated. The hollow ratio is represented by the average value of the hollow ratio of 20 fibers.
(I-4) Average thickness (in the case of film-like sheet)
Using a peacock with a stylus with a diameter of 8 mm, the thickness under the condition of a load of 1.25 N / cm ² was measured. The measurement was performed at three points at both ends and the center of the film, and the average value of these points was taken as the average thickness.
(II) Evaluation of Laminated Body and Fiber Reinforced Resin Composite (II-1) Moldability The laminates obtained in Examples and Comparative Examples were inserted into a preheated hot press, and the temperature was 250 ° C. and the pressing time was 10 minutes. Under the above conditions, the molding processability when molding the fiber-reinforced resin composite under the press pressure of 15 MPa was evaluated according to the following criteria.

◯: No gas is generated during molding, and a molded product with a good surface appearance can be obtained. △: A little gas is generated during molding, but it does not affect the surface appearance. (II-2) Number of voids obtained The laminates obtained in Examples and Comparative Examples were inserted into a preheated hot press, and under the conditions (temperature, press time, press pressure) shown in Tables 3 to 5. A fiber reinforced resin composite was obtained. The cross section of the obtained fiber-reinforced resin composite was observed with a scanning electron microscope (SEM, manufactured by JEOL, JSM-6100) at a magnification of 100 times, and the number of voids was evaluated by the number of bubbles in the cross section. The size of the bubbles counts larger than the diameter of the reinforcing fibers, and if the number is 3 or less, the impregnation property of the resin into the reinforcing fibers is good.
(II-3) Bending elastic modulus The laminates obtained in Examples and Comparative Examples are inserted into a preheated hot press, and the fibers are subjected to the conditions (temperature, press time, press pressure) shown in Tables 3 to 5. A reinforced resin composite was obtained. From the obtained fiber-reinforced resin composite, a size of 80 mm in length and 10 mm in width was cut out as a sample piece, and the flexural modulus was measured in accordance with ISO178 (measurement conditions: test speed 2 mm / min, test temperature 23 ° C.). .. The sample pieces were cut out in two directions so that they were perpendicular to each other, and the flexural modulus was evaluated as the average value of the flexural modulus in the two directions.
(II-4) Bending strength A sample piece was prepared from the laminates obtained in Examples and Comparative Examples by the same method as in (II-2), and the bending strength was measured in accordance with ISO178 (measurement conditions: test). Speed 2 mm / min, test temperature 23 ° C). The sample pieces were cut out in two directions so that they were perpendicular to each other, and the bending strength was evaluated as the average value of the bending strengths in the two directions.
(II-5) Appearance A sample piece similar to the laminate (II-2) obtained in Examples and Comparative Examples was prepared, the sample was visually confirmed, and the evaluation was made according to the following criteria.

〇: The fibers are evenly laminated and the surface appearance is good.

△: Fibers are partially unevenly laminated, but do not affect the surface appearance.

X: The fibers are non-uniformly laminated and the surface appearance is poor.
[Composition used]
In the examples, the following components were used.
(Component A) (Polypropylene resin)
A-1: Homopolypropylene resin [“VS200A” manufactured by SunAllomer Ltd., MFR (230 ° C., 2.16 kg load) = 0.5 g / 10 min]
A-2: Homopolypropylene resin ["Prime Polypropylene J105G" manufactured by Prime Polymer Co., Ltd., MFR (230 ° C, 2.16 kg load) = 9 g / 10 min]
(B component) (polycarbonate resin)
B-1: Polycarbonate resin composed of 2,2-bis (4-hydroxyphenyl) propane as a monomer component [MVR (300 ° C., 1.2 kg load) = 8.5 cm ^3/10 min]
B-2: Copolymerized polycarbonate composed of 2,2-bis (4-hydroxyphenyl) propane as a monomer component and a polydiorganosiloxane compound represented by the following formula [14] (average number of repetitions p in the formula p = about 37). Resin [MVR (300 ° C, 1.2 kg load) = 5.5 cm ^3/10 min, polycarbonate siloxane component content 8.2%]

(C component: modified polyolefin resin)
C-1: Maleic anhydride-modified polypropylene resin [manufactured by Mitsubishi Chemical Corporation, "SCONA TPPP 9212GA" (product name)]
C-2: Acid-modified olefin wax which is a copolymer of maleic anhydride and α-olefin ["Diacarna DC30M" (product name) manufactured by Mitsubishi Chemical Corporation]
(D component: styrene-based thermoplastic elastomer)
D-1: Styrene-ethylene / propylene-styrene block copolymer [Styrene content: 65 wt%, MFR: 0.4 g / 10 min, Septon 2104 manufactured by Kuraray Co., Ltd. (product name)]
(Reinforcing fiber)
FI-1: Carbon fiber unidirectional tape ["F-22" manufactured by Toho Tenax Co., Ltd., fiber diameter = 7 μm]
FI-2: Carbon fiber woven fabric ["W3101" manufactured by Toho Tenax Co., Ltd., basis weight = 200 g / m ² , thickness 0.25 mm, fiber diameter = 7 μm]
FI-3: Nickel coated carbon fiber tape ["HTS40 MC" manufactured by Toho Tenax Co., Ltd., fiber diameter = 7.5 μm, width 10 mm]
FI-4: Glass fiber woven fabric ["WF150" manufactured by Nitto Boseki Co., Ltd., grain = 144 g / m ² , thickness 0.22 mm, fiber diameter = 13 μm]
FI-5: Aramid fiber non-woven fabric ["Technora EF200" manufactured by Teijin Limited, basis weight = 200 g / m ² , fiber diameter = 12 μm]
FI-6: Carbon fiber sheet [manufactured by Toho Tenax Co., Ltd .: HT C422 6 mm, major axis 7 μm, cut length 6 mm, carbon fiber is pressed to form a sheet with a width of 300 mm and a length of 300 mm]
[Manufacturing Examples 1-9, 11-14] (Manufacturing of a sheet composed of thermoplastic resin fibers)
The polypropylene resin composition shown in Table 1 was dried at 80 ° C. for 5 hours in a hot air circulation type dryer, and then nitrogen gas was melt-mixed as a foaming agent (nitrogen filling pressure = 3 MPa) from a twin-screw extruder. It was extruded at the extrusion temperature shown in the table, taken up at the spinning speed shown in the table while quenching at the die outlet, and wound up as a hollow mesh fiber sheet. The evaluation of this hollow mesh fiber sheet is shown in Table 1.
[Manufacturing Example 10] (Manufacturing of thermoplastic resin sheet (film))
The polypropylene tree composition shown in Table 1 is dried at 80 ° C. for 5 hours in a hot air circulation type dryer, then extruded from a twin-screw extruder at the extrusion temperature shown in the table, and rapidly cooled at the die outlet to be shown in the table. A film-shaped thermoplastic resin sheet having the stated thickness was prepared. The evaluation of this film-like sheet is shown in Table 1.
[Manufacturing Example 15]
The polypropylene resin composition shown in Table 1 was dried at 80 ° C. for 5 hours in a hot air circulation type dryer, and then nitrogen gas was melt-mixed as a foaming agent (nitrogen filling pressure = 3 MPa) from a twin-screw extruder. It was extruded at the extrusion temperature shown in the table, taken up at the spinning speed shown in the table while quenching at the die outlet, and wound up as a hollow mesh fiber sheet. Seven of the obtained hollow mesh fiber sheets were laminated and sent out by a belt, and the fibers were spread in the horizontal direction at a spreading magnification of 7 times while grasping both ends thereof, and then heat-treated at 150 ° C. and wound up. The evaluation of this hollow mesh fiber sheet is shown in Table 1.
[Examples 1 to 18, Comparative Examples 1 to 6]
The thermoplastic resin sheets and reinforcing fiber sheets obtained in Production Examples 1 to 15 were laminated in the proportions shown in Tables 2 and 3 to form a laminated body.

The laminate was inserted into a preheated hot press to obtain a fiber reinforced resin composite (FRP molded product) under the press conditions (temperature, press time, press pressure) shown in Tables 2 and 3. At the time of laminating, care should be taken not to bias the reinforcing fibers, and the thickness of the fiber-reinforced resin composite should be the amount of the thermoplastic fiber sheet and the reinforcing fibers so that the desired thickness is obtained after heating and pressurizing in advance. Was adjusted. The evaluation of the finally obtained fiber reinforced resin composite is shown in Tables 2 and 3.

1. 1. Deformed fiber cross section 2. Bubbles 3. Circumscribed circle 4. Inscribed circle 5. Thermoplastic resin sheet layer 6. Reinforcing fiber sheet layer

Claims

A laminate of a reinforcing fiber sheet and a thermoplastic resin sheet, wherein the thermoplastic resin sheet is (A) 1 to 99 parts by weight of a polypropylene resin (A component) and (B) 99 to 1 parts of a polycarbonate resin (B component). A resin composition containing 0.1 to 900 parts by weight of the (C) modified polyolefin resin (C component) with respect to 100 parts by weight of the resin component composed of parts by weight, and the reinforcing fiber constituting the reinforcing fiber sheet. A laminate characterized in that the content is 151 to 900 parts by weight with respect to 100 parts by weight of the resin component composed of the A component and the B component.
The laminate according to claim 1, wherein the component B is a polycarbonate resin containing 1 to 100 mol% of the carbonate constituent units represented by the following formula [1] in the total carbonate constituent units.

[In the above general formula [1], R 1 and R 2 are independently hydrogen atom, halogen atom, alkyl group having 1 to 18 carbon atoms, alkoxy group having 1 to 18 carbon atoms, and 6 to 6 carbon atoms, respectively. 20 cycloalkyl groups, cycloalkoxy groups with 6 to 20 carbon atoms, alkenyl groups with 2 to 10 carbon atoms, aryl groups with 6 to 14 carbon atoms, aryloxy groups with 6 to 14 carbon atoms, carbon atoms Represents a group selected from the group consisting of an aralkyl group having a number of 7 to 20 and an aralkyloxy group having 7 to 20 carbon atoms, a nitro group, an aldehyde group, a cyano group and a carboxyl group. A and b are each an integer of 1 to 4, and W is at least one group selected from the group consisting of a single bond or a group represented by the following general formula [2].

(In the above general formula [2], R 11 , R 12 , R 13 , R 14 , R 15 , R 16 , R 17 and R 18 are independently hydrogen atoms, alkyl groups having 1 to 18 carbon atoms, and carbon atoms, respectively. Represents a group selected from the group consisting of an aryl group having a number of 6 to 14 and an aralkyl group having a carbon atom number of 7 to 20, and R 19 and R 20 independently represent a hydrogen atom, a halogen atom, and an alkyl having 1 to 18 carbon atoms. Group, alkoxy group with 1 to 10 carbon atoms, cycloalkyl group with 6 to 20 carbon atoms, cycloalkoxy group with 6 to 20 carbon atoms, alkenyl group with 2 to 10 carbon atoms, 6 to 14 carbon atoms A group consisting of an aryl group, an aryloxy group having 6 to 10 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, an aralkyloxy group having 7 to 20 carbon atoms, a nitro group, an aldehyde group, a cyano group and a carboxyl group. Represents a group selected from, and R 21 , R 22 , R 23 , R 24 , R 25 and R 26 are independently hydrogen atoms, alkyl groups having 1 to 12 carbon atoms, or substituted or unsubstituted groups having 6 to 12 carbon atoms, respectively. If there are a plurality of aryl groups, they may be the same or different, c is an integer of 1 to 10, d is an integer of 4 to 7, e is a natural number, and f is 0 or a natural number. Yes, e + f is a natural number of 150 or less, and X is a divalent aliphatic group having 2 to 8 carbon atoms.)]
The laminate according to claim 1 or 2, wherein the C component is maleic anhydride-modified polypropylene.
The resin composition constituting the thermoplastic resin sheet further contains (D) a styrene-based thermoplastic elastomer (component D) in an amount of 1 to 20 parts by weight based on 100 parts by weight of the resin component composed of the component A and the component B. The laminate according to any one of claims 1 to 3, which is characterized.
The laminate according to any one of claims 1 to 4, wherein the reinforcing fiber sheet is one of a woven or knitted fabric, a non-woven fabric, and a unidirectional sheet.
The laminate according to any one of claims 1 to 5, wherein the fiber constituting the reinforcing fiber sheet is at least one kind of fiber selected from carbon fiber and glass fiber.
The fiber constituting the reinforcing fiber sheet has a surface oxygen concentration (O / C) of 0. The laminate according to claim 6, wherein the carbon fiber is 15 or more.
The laminate according to any one of claims 1 to 7, wherein the thermoplastic resin sheet is made of a mesh-like hollow fiber.
A fiber-reinforced resin complex composed of the laminate according to any one of claims 1 to 8.
The laminate according to any one of claims 1 to 8 is placed at a temperature equal to or higher than the melting temperature of the thermoplastic resin constituting the thermoplastic resin sheet and lower than the heat resistant temperature of the reinforcing fiber constituting the reinforcing fiber sheet. A method for producing a fiber-reinforced resin composite, which comprises a pressure treatment.