JPH0995607A - Transparent glass-reinforcing resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a transparent class-reinforcing resin composition having improved transparency while keeping high rigidity. SOLUTION: This resin composition is obtained by compounding 100 pts.wt. of the total of (A) (a-1) a polycarbonate resin and/or (a-2) a polyester carbonate resin and (B) a polyester resin, (C) 5-150 pts.wt. of a glass filter having a refractive index difference to the component (A) of <=0.01 and (D) 0.000005-0.5 pts.wt. of a catalyst of a basic compound and/or a Lewis acid compound except a protonic acid.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a glass reinforced resin composition, and more particularly to a transparent glass reinforced resin composition having high rigidity.

[0002]

2. Description of the Related Art Polycarbonate resins are excellent in transparency, heat resistance and impact resistance, and are therefore used as an alternative material for glass for optical applications such as lenses and prisms. However, since it has lower rigidity than glass, physical properties are improved by adding an appropriate filler such as glass fiber in applications requiring high rigidity.

However, when a glass filler or the like is added, the refractive index of glass (usually about 1.545 for conventional glass) and the refractive index of polycarbonate resin (usually about 1.582 for conventional polycarbonate resin). However, there is a disadvantage that the transparency, which is a major characteristic of the polycarbonate resin, is impaired due to the large difference between

[0004]

SUMMARY OF THE INVENTION It is an object of the present invention to solve the drawbacks of the conventional method and to provide a glass-reinforced resin composition having improved transparency while maintaining high rigidity.

[0005]

The present invention positively promotes a transesterification reaction between a polyester resin and a polycarbonate resin, which is added to reduce the difference between the refractive index of a polycarbonate resin and the refractive index of glass. By improving the transparency of the resin composition before the glass filler is mixed, the transparency after the glass filler is mixed is improved.

That is, component A) a-1) polycarbonate resin and / or a-2) polyester carbonate resin, and component B) polyester resin to 100 parts by weight in total, C) the refractive index of the resin of component A). The difference is 0.
5 to 150 parts by weight of a glass filler of 01 or less, and D)
It is a transparent glass-reinforced resin composition in which a basic compound catalyst and / or a Lewis acidic compound catalyst excluding a protonic acid is mixed with 0.000005 to 0.5 part by weight.

Further, with respect to 100 parts by weight in total of the components A) a-1) polycarbonate resin and / or a-2) polyester carbonate resin, and B) polyester resin, the difference in refractive index from C) resin A) is 0. A transparent glass-reinforced resin composition can be obtained by blending 5 to 150 parts by weight of a glass filler of 0.01 or less and 0.0001 to 1 part by weight of E) a protonic acid and / or a derivative thereof.

With respect to a total of 100 parts by weight of component A) a-1) polycarbonate resin and / or a-2) polyester carbonate resin, and component B) polyester resin, the difference in refractive index from C) resin A) is 0. A transparent glass-reinforced resin composition can be obtained by mixing 5 to 150 parts by weight of a glass filler of 01 or less and 0.001 to 5 parts by weight of F) a compound having two or more phenolic hydroxyl groups.

Further, the component A) a in each of the above-mentioned constitutions
As the polycarbonate resin of -1), a polycarbonate resin having terminal hydroxyl groups of 5 to 100% of all terminals can be used.

Incidentally, the component A) a- in each of the above-mentioned constitutions
As the polycarbonate resin of 1), it is possible to use a polycarbonate resin having terminal hydroxyl groups of 10 to 100% of all terminals.

Component A) a- in each of the above-mentioned constitutions
As the polycarbonate resin of 1), a polycarbonate resin having 20 to 100% of all terminal hydroxyl groups can be used.

In each of the above-mentioned constitutions, the respective composition ratios of the resin component of the component A) and the resin component of the component B) are 99 to 10 parts by weight for the component A) and 1 to 90 for the component B).
It can be by weight.

In each of the above-mentioned constitutions, the respective composition ratios of the resin component of the component A) and the resin component of the component B) are 79 to 20 parts by weight for the component A) and 21 to 8 for the component B).
It can be 0 parts by weight.

In each of the above-mentioned constitutions, the respective composition ratios of the resin component of component A) and the resin component of component B) are 66 to 20 parts by weight for component A) and 34 to 8 for component B).
It can be 0 parts by weight.

In each of the above constitutions, the component B) is
Polyethylene terephthalate, polybutylene terephthalate, cyclohexanedimethanol terephthalate, copolyester of cyclohexanedimethanol and terephthalic acid / isophthalic acid, polyester selected from the group of polyethylene naphthalate, polybutylene naphthalate, or a combination of two or more thereof. Can consist of:

The above-mentioned component A) a-1) polycarbonate is an aromatic homopolycarbonate or copolycarbonate produced by reacting a dihydric phenol with a carbonate precursor. Further, the polycarbonate of the present invention may be branched. Such branched polycarbonates are obtained as branched thermoplastic branched polycarbonates by reacting a polyfunctional aromatic compound with a dihydric phenol and a carbonate precursor.

The method for producing the polycarbonate of the present invention is known per se, and a method for synthesizing a polycarbonate by a transesterification reaction of a dihydric phenol and a carbonic acid diester in a molten state, or a dihydric phenol and phosgene are reacted in a solution Methods (particularly the interface method) are known.

For example, JP-A-2-175723 and JP-A-2-12493
4, U.S. Patent Nos. 4,001,184, 4,238,569, 4,23
It is described in No. 8,597 and No. 4,474,999.

The equivalent ratio adjustment of the terminal groups of the polycarbonate can be easily carried out by changing the molar ratio of the dihydric phenol as a raw material and the carbonic acid diester when producing the polycarbonate in the case of melt polymerization.

For example, when bisphenol A is used as the aromatic dihydroxy compound and diphenyl carbonate is used as the carbonic acid diester, the terminal group of the polycarbonate is a phenolic residue derived from bisphenol A and a phenyl group derived from diphenyl carbonate.
When the molar ratio of bisphenol A is increased, the equivalent ratio (I) / (II) of the phenolic terminal group (I) and the non-phenolic terminal group (II) in the produced polycarbonate increases.

The aromatic dihydroxy compound is not particularly limited, and various known compounds can be used. As an example, the following formula (Formula 1),

[0022]

Embedded image

(Wherein R ^a and R ^b are each independently a halogen or a monovalent hydrocarbon group, and X is —C (R ^c ).
(R ^d )-, -C (= R ^e )-, -O-, ^-S- , -SO
- or -SO ₂ - and and, R ^c and R ^d are independently a hydrogen atom or a monovalent hydrocarbon group, R ^e is a divalent hydrocarbon group, p and q are each independently Represents an integer of 0 to 4. d is a compound represented by 0 or an integer of 1.

For example, bis (4-hydroxyphenyl)
Methane, 1,1-bis (4-hydroxyphenyl) ethane, 2,2-bis (4-hydroxyphenyl) propane,
2,2-bis (4-hydroxyphenyl) butane, 2,2-bis (4-hydroxyphenyl) octane, bis (4-hydroxyphenyl) phenylmethane, 2,2-bis (4-hydroxy-3-methylphenyl) Propane, 2,2 bis (4
-Hydroxy-3,5-dimethylphenyl) propane,
1,1-bis (4-hydroxy-t-butylphenyl) propane, 2,2-bis (4-hydroxy-3-bromophenyl) propane, 2,2-bis (4-hydroxy-3,5dibromophenyl) Bis (hydroxyaryl) alkanes such as propane; 1,1 bis (4-hydroxyphenyl)
Bis (hydroxyaryl) cycloalkanes such as cyclopentane and 1,1- (4-hydroxyphenyl) cyclohexane; 4,4′-dihydroxydiphenyl ether,
Dihydroxy aryl ethers such as bis (4-hydroxy-3-methylphenyl) ether; 4,4′-dihydroxydiphenyl sulfide, bis (4-hydroxy-3)
-Diphenyl diaryl sulfides such as -methylphenyl) sulfide; 4,4'-dihydroxydiphenyl sulfoxide, dihydroxydiaryl sulfoxides such as bis (4-hydroxy-3-methylphenyl) sulfoxide; 4,4'-dihydroxydiphenyl sulfone,
Examples thereof include, but are not limited to, dihydroxydiaryl sulfones such as bis (4-hydroxy-3-methylphenyl) sulfone; 4,4-biphenol and the like.

Of these, 2,2-bis (4-hydroxyphenyl) propane is particularly preferably used. In addition to the above, as the aromatic dihydroxy compound, the following general formula (Formula 2),

[0026]

Embedded image

(Here, each R ^f independently represents the carbon number 1 to
It is 10 hydrocarbon groups or a halogen compound or a halogen atom, and m is an integer of 0 to 4. For example, resorcinol, and 3-methylresorcinol, 3-ethylresorcinol, 3-propylresorcinol, 3-butylresorcinol, 3-tert-butylresorcinol,
3-phenylresorcinol, 3-cumylresorcinol, 2,3,
Substituted resorcinols such as 4,6-tetrafluororesorcin, 2,3,4,6-tetrabromoresorcin; catechol; hydroquinone, and 3-methylhydroquinone, 3-ethylhydroquinone, 3-propylhydroquinone, 3-butylhydroquinone, 3 -T-butylhydroquinone, 3
-Phenylhydroquinone, 3-cumylhydroquinone, 2,3,5,6-tetramethylhydroquinone, 2,3,
5,6-tetra-t-butylhydroquinone, 2,3,5,6
-Substituted fluoroquinone such as tetrafluorohydroquinone and 2,3,5,6-tetrabromohydroquinone, and the following formula (Formula 3),

[0028]

Embedded image

2,2,2 ', 2'-tetrahydro-3 represented by
3,3 ′, 3′-Tetramethyl-1,1′-spirobis (1H-indene) -7,7 ′ diol can also be used.

These aromatic dihydroxy compounds may be used alone or in combination of two or more kinds.

The carbonic acid diester is not particularly limited, and examples thereof include diphenyl carbonate, ditolyl carbonate, bis (chlorophenyl) carbonate, m-cresyl carbonate, dinaphthyl carbonate, bis (diphenyl) carbonate, diethyl carbonate, dimethyl carbonate, dibutyl. Examples thereof include, but are not limited to, carbonates and dicyclohexyl carbonates. Preferably, diphenyl carbonate is used.

These carbonates may be used alone or in combination of two or more.

In addition, a dicarboxylic acid or dicarboxylic acid ester may be contained as an acid component. Examples of dicarboxylic acids and dicarboxylic acid esters include aromatic dicarboxylic acids such as terephthalic acid, isophthalic acid, diphenyl terephthalate, diphenyl isophthalate; succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacin Aliphatic dicarboxylic acids such as acid, decandioic acid, dodecandioic acid, diphenyl sebacate, diphenyl decandioic acid, diphenyl dodecandioic acid; cyclopropanedicarboxylic acid, 1,2-cyclobutanedicarboxylic acid, 1,3-cyclobutanedicarboxylic acid , 1,
2′-cyclopentanedicarboxylic acid, 1,3-cyclopentanecarboxylic acid, 1,2-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, cyclopropanedicarboxylic acid diphenyl, 1, Diphenyl 2-cyclobutanedicarboxylate, diphenyl 1,3-cyclobutanedicarboxylate, 1,2
Alicyclic dicarboxylic acids such as diphenyl cyclopentanedicarboxylate, diphenyl 1,3-cyclopentanedicarboxylate, diphenyl 1,2-cyclohexanedicarboxylate and diphenyl 1,4-cyclohexanedicarboxylate.

These dicarboxylic acids or dicarboxylic acid esters may be used alone or in combination of two or more.

The dicarboxylic acid or dicarboxylic acid ester is contained in the above carbonic acid diester in an amount of preferably 50 mol% or less, more preferably 30 mol% or less.

In producing a polycarbonate, a polyfunctional compound having three or more functional groups in one molecule can be used together with an aromatic dihydroxy compound and a carbonic acid diester. As these polyfunctional compounds, compounds having a phenolic hydroxyl group or carboxyl are preferable, and compounds having three phenolic hydroxyl groups are particularly preferable.

Preferred specific examples of such compounds include 1,1,1-tris (4-hydroxyphenyl) ethane,
2,2 ', 2 "-tris (4-hydroxyphenyl) diisopropylbenzene, α-methyl-α, α', α'-tris (4-
Hydroxyphenyl) -1,4-diethylbenzene, α,
α ', α "tris (4-hydroxyphenyl) -1,3,5-triisopropylbenzene, phloroglysin, 4,6-dimethyl-2,4,6-tri (4-hydroxyphenyl) -heptane-2, 1,3,5-tri (4-hydroxyphenyl) benzene, 2,2-bis- (4,4- (4,4′-dihydroxyphenyl) -cyclohexyl) -propane, trimetic acid,
Examples include 3,5-benzenetricarboxylic acid and pyromellitic acid.

More preferably, 1,1,1-tris (4-hydroxyphenyl) ethane, α, α ', α "-tris (4-
(Hydroxyphenyl) -1,3,5-triisopropylbenzene or the like.

The polyfunctional compound is preferably 0.03 mol or less, more preferably 0.001 to 0.02 mol, and particularly preferably 0.01 to 0.02 mol based on 1 mol of the aromatic dihydroxy compound. It can be molar.

The polyester resin of component B) is a polyester of diol (or its ester-forming derivative) and dicarboxylic acid (or its ester-forming derivative), and the following compounds are used alone for both the diol component and dicarboxylic acid component. They may be used or may be used in combination.

Further, a compound having a hydroxyl group and a carboxylic acid group in one molecule such as lactone may be combined.

As the diol component, ethylene glycol, propylene 1,2-glycol, sun 1,6-diol,
Examples thereof include aliphatic diols having 2 to 15 carbon atoms such as octane 1,8-diol, neopentyl glycol, decane 1,10-diol, diethylene glycol and triethylene glycol. The preferred aliphatic diols are ethylene glycol and 1,4-butanediol.

Further, 1,2-cyclohexanediol, 1,4
-Cyclohexanediol, 1,4-cyclohexanedimethanol and the like can be mentioned. These cycloaliphatic diols can be used in either the cis or trans configuration or as a mixture of both. Suitable alicyclic diols are
It is 1,4-cyclohexanedimethanol.

Further, aromatic dihydric phenols such as resorcin, hydroquinone and naphthalene diol, polyethylene glycol having a molecular weight of 400 to 6000, polyglycols such as polypropylene glycol and polytetramethylene glycol, bisphenol A and bisphenol B, etc. The bisphenols described in No. -203956 can also be mentioned.

As the dicarboxylic acid component, isophthalic acid, terephthalic acid, orthophthalic acid, 2,2'-biphenyldicarboxylic acid, 3,3'-biphenyldicarboxylic acid, 4,4'-
Biphenyldicarboxylic acid, 4,4'-diphenyletherdicarboxylic acid, 1,5-naphthalenedicarboxylic acid, 1,4-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid and
Aromatic dicarboxylic acids such as 1,2-di (4-carboxyphenyl) ethane, adipic acid, succinic acid, oxalic acid, malonic acid, suberic acid, azelaic acid, sebacic acid, decanedicarboxylic acid, cyclohexanedicarboxylic acid and other aliphatic dicarboxylic acids And alicyclic dicarboxylic acids.

As the polyester resin of component B), these diols and dicarboxylic acids may be used alone, or two or more kinds of diols or dicarboxylic acids may be used in combination. The obtained polyesters may be used alone or in combination.

Polyesters, preferably polyesters of alkyldicarboxylic acids and aromatic diols or polyesters of aromatic dicarboxylic acids and alkylene glycols, specifically polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate,
Poly (1,4-cyclohexanedimethylene terephthalate), poly (1,4-cyclohexanedimethylene terephthalate-co-isophthalate), poly (1,4-butylene terephthalate-co-isophthalate), poly (ethylene-co-phthalate) 1,4-cyclohexanedimethylene terephthalate) and the like.

Regarding the glass filler of component C), the glass filler used in the present invention has a high refractive index and is preferably as close to polycarbonate as possible. Especially the refractive index is 1.57
It is preferably 6 to 1.590. Such glass fibers are commercially available from Asahi Fiber Glass Co., Ltd., for example, as ECR glasses. The glass filler is used in an amount of 1 to 60 parts by weight based on 99 to 40 parts by weight of the component (A). If the amount of the glass filler is too small, sufficient rigidity will not be exhibited, and if it is too large, the strand will not be stable when melted, which is not preferable.

As the form, for example, glass fiber, milled glass, glass beads, glass flakes, glass powder and the like can be used, and these may be used alone or in combination of two or more kinds.

A coupling agent such as aminosilane or epoxysilane can be used to improve the adhesion between the glass filler and the resin. Further, in the case of glass fiber, an epoxy-based or urethane-based binder can be used as a suitable binder.

The difference in refractive index between the above components A) and C) is 0.01 or less, preferably 0.005 or less. If the difference is larger than 0.01, the transparency of the resin composition is lowered and it becomes impractical.

Since the glass-reinforced polycarbonate resin composition of the present invention has high transparency while maintaining rigidity, it can be advantageously used not only for optical applications such as lenses and prisms, but also because it is lightweight, Can be used as a glass substitute for sunroofs, windows, greenhouses, etc.

Regarding the catalyst component of component D), a catalyst known as a transesterification catalyst can be used. For example, Lewis acid catalysts include tin compounds such as dibutyltin oxide, tin oxalate, tin acetate, tin oxide, tetrabutoxy titanium, tetraphenoxy titanium, titanium oxide, titanium compounds such as titanium oxalate, antimony trioxide, antimony tartrate oxide, etc. Antimony compounds, zinc compounds such as zinc acetate, zinc stearate, zinc acetylacetone,
Boric acid compounds such as triphenoxyboron and zinc borate,
Examples thereof include germanium compounds such as germanium oxide and germanium ethoxide, manganese acetate, and cobalt acetate.

Examples of the basic compound catalyst include organic basic compounds, alkalis, alkaline earth metals and the like. Examples of the basic compound catalyst are shown below. 1) Organic Basic Compound Pyrolytic Nitrogen-containing Basic Compound Tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrabutylammonium hydroxide, tetraphenylammonium hydroxide, and other ammonium hydroxides having an alkyl or aryl group, and Examples thereof include salts with acids weaker than PKa4.

Nitrogen-containing basic compounds other than the above: Tertiary amines such as trimethylamine, triethylamine, trioctylamine, triphenylamine and dibenzylmethylamine, NHR ₂ (wherein R is methyl, ethyl, phenyl, benzyl, toluyl) Secondary amines, such as alkyl, aryl groups, etc., NRH
Examples thereof include primary amines represented by ₂ (in the formula, R is the same as above), pyridine, methylpyridine, methoxypyridine, quinoline, imidazole and ammonia.

2) Alkali or alkaline earth metal inorganic compounds Hydroxides, hydrides, amides, carbonates of alkali metals such as sodium, potassium, lithium and cesium and alkaline earth metals such as calcium, magnesium and barium, Examples thereof include phosphate and borate.

Salts with organic acids Metal amides of alkali metals such as sodium, potassium, lithium and cesium and alkaline earth metals such as calcium, magnesium and barium, carboxylates, salts with phenolic hydroxyl groups, alcohols Examples thereof include salts with hydroxyl groups and chelate compounds with acetylacetone and the like.

The transesterification catalyst (component C)) is preferably in the range of 1 ppm to 50000 ppm, more preferably 10 ppm to 1000 ppm in the case of Lewis acid catalyst, relative to 100 parts by weight of components A) and B) in total. Is.
In the case of a basic catalyst, 0.05 to 10000 pp
m, preferably 0.05 to 100 ppm, more preferably 0.1 to 10 ppm.

If the amount of the catalyst is less than the above range, the effect of addition does not appear, and if it is more than the above range, the molecular weight decreases during kneading and the physical properties decrease.

With respect to the component E), any protic acid and / or its derivative is effective. Examples of the derivative include a compound that exhibits acidity during granulation due to heat or a reaction with a resin, such as an ester of sulfonic acid, an ammonium salt of a strong acid, or a metal salt. Further, when the acid is a dibasic acid or more, it may be a partial esterified compound or a partial metal salt. These acidic compounds may be used alone or in a mixture.

As the protic acid, various acids can be mentioned. For example, phenol, phenols such as cresol and xylenol, 2,4 dinitrophenol,
Phenols having electron-withdrawing groups such as 2,4,6 trinitrophenol as substituents, carboxylic acids such as formic acid, methoxyacetic acid, acetic acid, butyric acid, citric acid, malic acid, trifluoroacetic acid, trichloroacetic acid, 1,1- Carboxylic acids having an electron-withdrawing group at the α-position such as difluoropropionic acid, monochloroacetic acid, dichloroacetic acid, monofluoroacetic acid, nitroacetic acid and cyanoacetic acid, m-nitrobenzoic acid, 2,4 dinitrobenzoic acid and 2,4,6 Aromatic carboxylic acids having an electron-withdrawing group as a substituent such as trinitrobenzoic acid, oxalic acid, 2-carboxypropionic acid, malonic acid, succinic acid, fumaric acid, dicarboxylic acids such as maleic acid, phthalic acid, isophthalic acid, terephthalic acid And aromatic dicarboxylic acids such as 1,3 naphthalene dicarboxylic acid, boric acid, hydrobromic acid, nitric acid, and iodo acid,
Inorganic acids such as perchloric acid, periodate, bromic acid and sulfuric acid,
Benzenesulfonic acid, p-toluenesulfonic acid, naphthalenesulfonic acid, sulfonic acids such as methylsulfonic acid and fluorosulfonic acid, phosphoric acid, phosphorous acid, hypophosphorous acid, pyrophosphoric acid, metaphosphoric acid and polyphosphoric acid and the like. be able to.

Examples of the ester derivative include methyl benzenesulfonate, ethyl benzenesulfonate, butyl benzenesulfonate, butyl p-toluenesulfonate, phenyl p-toluenesulfonate, benzyl p-toluenesulfonate, and butyl naphthalenesulfonate. And sulfonic acid esters such as butyl methyl sulfonate, monophosphate (2,4 ditertiary butylphenyl), diphosphate (2,4 ditertiary butylphenyl), monophenyl phosphite, dimethyl phosphate, diphosphate (2,4) 4 dimethylphenyl) and mono- and diesters such as diethyl phosphite and dimethylsulfate.

Examples of the salt derivative consisting of the protonic acid and the nitrogen-containing basic compound include, for example, alkyls such as tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrabutylammonium hydroxide and tetraphenylammonium hydroxide, Ammonium hydroxides having an aryl group, tertiary amines such as trimethylamine, triethylamine, trioctylamine, triphenylamine and dibenzylmethylamine, NHR2 (wherein R is methyl, ethyl, phenyl, benzyl, toluyl, etc. Secondary amines represented by alkyl, aryl groups, etc.), primary amines represented by NRH2 (wherein R is the same as above), pyridine, methylpyridine, methoxypyridine, quinoline, a It can be mentioned salts such as the imidazole and ammonia.

Further, as the metal salt derivative, for example,
Monosodium carbonate, monosodium phosphate, disodium phosphate, monopotassium phosphate, dilithium phosphate, magnesium phosphate, monosodium phosphite, disodium phosphite, monopotassium phosphite, dilithium phosphite, calcium phosphate, monosodium oxalate, phthalic acid Monopotassium,
Examples thereof include sodium borate, monopotassium sulfate, and lithium paratoluenesulfonate.

Component E) is a resin component (component A) a-1), a
-2) and 100 parts by weight of component B)).
If it is less than 000005 parts by weight, the effect of addition does not appear,
If it is more than 0.5 parts by weight, the resin component is adversely affected during granulation and molding, and the mechanical strength is lowered, which is not preferable.

As the compound F) having two or more phenolic hydroxyl groups, for example, the following general formula (Formula 4),

[0067]

Embedded image

In the formula, R is a hydrogen atom, a halogen atom (for example, chlorine, bromine, fluorine, iodine) or an alkyl group having 1 to 8 carbon atoms, and when there are plural Rs, they may be the same. They may be different, and n and m are numbers from 0 to 4. Further, X is a single bond, an alkylene group having 1 to 8 carbon atoms, an alkylidene group having 2 to 8 carbon atoms, or 5 to 15 carbon atoms.
Cycloalkylene group, a cycloalkylidene group having 5 to 15 carbon atoms, or -S-, -SO-, -SO2-, -C
An O-, -O- bond or a bond represented by the general formula (Formula 5) is shown.

[0069]

Embedded image Is a compound having a phenolic hydroxyl group having the structure represented by

Examples of such dihydric phenols include bis (4 hydroxyphenyl) methane and 1,1 bis (4
Hydroxyphenyl) ethane, 1,2 bis (4hydroxyphenyl) ethane, bis (4hydroxyphenyl) phenylmethane, bis (4hydroxyphenyl) diphenylmethane, 2,2 bis (4hydroxyphenyl) propane, 2,2
Bis (4hydroxyphenyl) butane, 1,1 bis (4hydroxyphenyl) cyclohexane, bis (3,5dimethyl-4hydroxyphenyl) methane, 1,1 bis (3,5dimethyl-4hydroxyphenyl) ethane, 1, 2bis (3,5dimethyl-4hydroxyphenyl) ethane, 2,2bis (3,5dimethyl-4hydroxyphenyl) propane, 2,2bis (3,5
5 dimethyl-4-hydroxyphenyl) butane, bis (3,5
-Dimethyl-4-hydroxyphenyl) phenylmethane,
Bis (3,5dimethyl-4hydroxyphenyl) diphenylmethane, bis (3,5dichloro-4hydroxyphenyl) methane, 2,2bis (3,5dichloro-4hydroxyphenyl)
Methane, bis (3,5dibromo-4hydroxyphenyl) methane, 2,2bis (3,5dibromo-4hydroxyphenyl)
Dihydroxyarylalkanes such as propane, dihydroxyarylsulfones such as bis (4hydroxyphenyl) sulfone, bis (3,5dimethyl-4hydroxyphenyl) sulfone, bis (3,5dibromo-4hydroxyphenyl) sulfone, bis ( Dihydroxy aryl ethers such as 4-hydroxyphenyl) ether, bis (3,5dimethyl-4hydroxyphenyl) ether, bis (3,5dibromo-4hydroxyphenyl) ether, bis (4hydroxyphenyl) sulfide, bis (3, Dihydroxyaryl sulfides such as 5-dimethyl-4hydroxyphenyl) sulfide and bis (3,5dibromo-4hydroxyphenyl) sulfide, dihydroxyarylketones such as 4,4′dihydroxybenzophenone, and bis (4hydroxyphenyl) sulfone. Mention may be made of a sulfoxide such as Sid.

Also, dihydroxybenzenes such as hydroquinone, resorcin, methylhydroquinone, 1,4 dihydroxynaphthalene, 1,5 dihydroxynaphthalene, 2,6
Examples thereof include dihydroxynaphthalenes such as dihydroxynaphthalene, 3,6 dihydroxyxanthene, and 3,6 dihydroxyxanthone.

Examples of the compound having a trivalent or higher phenolic hydroxyl group include tris (4hydroxyphenyl) methane, tris (3,5dimethyl-4hydroxyphenyl) methane and 1,3,5-tris (4 Examples thereof include hydroxyphenyl) benzene and the like.

Furthermore, a polycarbonate oligomer having a molecular weight of 5000 or less and having a phenolic hydroxyl group using a dicarboxylic acid and a carbonyl precursor, for example, phosgene or diphenyl carbonate at the terminal, or a phenolic hydroxyl group using a dicarboxylic acid is terminated. And a polyester oligomer having a molecular weight of 500 or less can be mentioned.

These divalent and trivalent phenols may be used alone or in admixture of two or more.

Component F) is 0.001 to 5 parts by weight, preferably 0.002 to 1 part by weight, based on 100 parts by weight of the resin.
Parts by weight, more preferably 0.005 to 0.1 parts by weight. If less than 0.001 parts by weight, the addition effect does not appear, and if more than 5 parts by weight, the mechanical strength decreases due to a decrease in the molecular weight of the resin component. And bleeding out from the molded product is not preferable.

To the transparent glass-reinforced resin composition of the present invention, a light diffusing agent, an infrared absorbing agent or the like can be added as an additive depending on the optical use. Examples of the former include calcium carbonate and polymethylmethacrylate (PMMA)
Examples thereof include crosslinked fine particles. Furthermore, pigments, dyes, reinforcing agents, fillers, flame retardants, stabilizers (heat resistance, oxidation resistance, weather resistance, etc.), lubricants, release agents, plasticizers, antistatic agents, etc., within the range not impairing the spirit of the present invention. May be included.

Examples of flame retardants for such resin compositions include bromo compounds, antimony trioxide, antimony phosphate, and phosphoric acid esters. Also,
Examples of the stabilizer include phosphorus stabilizers such as tris (2,4
-Ditertiarybutylphenyl) phosphite, tri (nolylphenyl) phosphite, and other hindered phenolic stabilizers such as Irgafos 1010, and benzotriazole-based stabilizers such as UV5411;
For tinuvin 234 and the like, and thiols and epoxy-based stabilizers, Celoxide 2021P, Denacol EX1
92, epoxidized linseed oil and the like.

As the antistatic agent, polyethylene glycol, polypropylene glycol, modified products or copolymers thereof, or salts thereof, such as metal salts of sulfonic acid or phosnium salts (EPA202 (trade name); Takemoto Yushi Co., Ltd.) Manufactured) and the like.

In the method for producing the resin composition of the present invention, the above-mentioned respective components A) to F) are blended as necessary, and the resin components A) and B) are successively kneaded with the components D) to F). After that, the glass of the component C) may be blended and kneaded, or all the components may be blended and kneaded at the same time. By doing so, a desired resin composition can be obtained.

Then, methods usually used for such compounding and kneading, for example, ribbon blender, Henschel mixer, Banbury mixer, drum tumbler, single-screw extruder, twin-screw extruder, co-kneader, multi-screw extrusion are used. It can be performed using a machine or the like.

The heating temperature during kneading is usually 250 to
It is selected in the range of 300 ° C. Polycarbonate resin composition thus obtained, various known molding methods, for example,
Injection molding, blow molding, extrusion molding, compression molding, calender molding, rotational molding and the like can be applied.

If necessary, a film insert molding in which a transparent plastic film is first inserted into a mold is appropriately carried out, so that molded articles such as a window for a ship / vehicle, a sunroof, a construction field or a home appliance field. It can be a molded article or the like.

Measurement method Hue (YI): x, y, and z values were measured by an transmission method on an injection molded plate (thickness: 3 mm) using ND-1001DP of Nippon Denshoku Industries Co., Ltd. Yellowness index (YI) was determined. YI = (1.277X-1.060Z) * 100 / Y haze, light transmittance: NDH-200 manufactured by Nippon Denshoku Industries Co., Ltd. was used to measure the haze of an injection-molded plate (thickness: 3 mm). Kneading and granulation: A single-screw extruder VC65 (cylinder diameter 65 mmφ, full flight screw) manufactured by Tezuka Seisakusho KK was used to extrude at a cylinder temperature of 300 ° C. and pelletize. Injection molding: PS60E9ASE type injection molding machine manufactured by Nissei Plastic Industry Co., Ltd. was used to mold at a cylinder temperature of 300 ° C and a mold temperature of 80 ° C to obtain a test piece.

[0084]

BEST MODE FOR CARRYING OUT THE INVENTION

Example 1 Polycarbonate resin (Lexan (trademark): terminal hydroxyl group ratio 0%, manufactured by GE Plastics Co., Ltd.)
6.3 kg, polybutylene terephthalate resin (Barox (trademark), Japan GE Plastics Co., Ltd.)
2.7 kg, ECR glass fiber (manufactured by Asahi Fiber Glass Co., Ltd.) 1.0 kg and bisphenol A 9 g were pelletized by an extruder. This pellet was injection-molded to prepare a test piece. Table 1 shows the evaluation results.

Examples 2 to 7 Test pieces were prepared in the same manner as in Example 1 except that the polycarbonate resin, polybutylene terephthalate resin, glass filler, phenolic compound, esterification catalyst and acidic substance were used in the compounding ratios shown in Table 2. It was created. The evaluation results are shown in Table 1 together with the compounding ratio. The abbreviations and compound formulas in the table are
BPA: bisphenol A, Me ₄ NOH: tetramethylammonium hydroxide, Ti (OBu) ₄ : titanium tetrabutoxide, H ₃ PO ₃ : phosphorous acid, NaH ₂ PO ₃ : monosodium phosphite, pTsOBu: paratoluene sulfone Butyl acid,
pTsOH: represents paratoluenesulfonic acid.

[0086]

[Table 1]

Example 8 Polycarbonate resin (Lexan ™: 65% terminal hydroxyl group, manufactured by GE Plastics Co., Ltd.) 9
kg, polybutylene terephthalate resin (Barox (trademark): Japan GE Plastics Co., Ltd.) 1 kg, and ECR glass fiber (Asahi Fiber Glass Co., Ltd.)
1 kg was extruded into pellets with an extruder. This pellet was injection molded to prepare a test piece. The evaluation results are shown in Table 2.

Examples 9 to 13 Test pieces were prepared in the same manner as in Example 9 except that the polycarbonate resin, polybutylene terephthalate resin, glass filler, phenolic compound, esterification catalyst and acidic substance were used in the compounding ratios shown in Table 2. It was created. The evaluation results are shown in Table 2 together with the compounding ratio.

[0089]

[Table 2]

Example 14 Polycarbonate resin (Lexan ™: 35% terminal hydroxyl group, manufactured by GE Plastics Co., Ltd.) 7
kg, Kodar A150 (trademark: manufactured by Eastman Kodak Co., Ltd.), 3 kg of ECR glass fiber (manufactured by Asahi Fiber Glass Co., Ltd.) and 2.7 g of phosphorous acid (H ₃ PO ₃ ) were pelletized by an extruder. This pellet was injection molded to prepare a test piece. The evaluation results are shown in Table 3.

Example 15 Polycarbonate resin (Lexan (trademark): 35% terminal hydroxyl group, manufactured by GE Plastics Co., Ltd.) 8
kg, polycyclohexanedimethanol terephthalate (synthetic product) 2 kg, ECR glass fiber (made by Asahi Fiber Glass Co., Ltd.) 1 kg, tetramethylammonium hydroxide (Me ₄ NOH) 0.45 g and monosodium phosphite (N
aH ₂ PO ₃ ) was pelletized in the extruder. This pellet was injection molded to prepare a test piece. The evaluation results are shown in Table 3.

Example 16 Polycarbonate resin (Lexan (trademark): 35% terminal hydroxyl group, manufactured by GE Plastics Co., Ltd.) 6
kg, polycyclohexanedimethanol terephthalate (synthetic product) 4 kg, ECR glass fiber (made by Asahi Fiber Glass Co., Ltd.) 1 kg, tetramethylammonium hydroxide (Me ₄ NOH) 0.45 g and phosphorous acid 2.7 g with an extruder. Pelletized. This pellet was injection molded to prepare a test piece. The evaluation results are shown in Table 3.

Example 17 Polycarbonate resin (Lexan ™: 35% terminal hydroxyl group, manufactured by GE Plastics Co., Ltd.) 9
kg, polyethylene terephthalate resin (Mitsui PET (trademark), manufactured by Mitsui Petrochemical Co., Ltd.) 1 kg, ECR glass fiber (manufactured by Asahi Fiber Glass Co., Ltd.) 1 kg, bisphenol A 7.2 g, sodium stearate 0.09 g and para 0.27 g of butyl toluenesulfonate (pTsOBu) was pelletized in the extruder. This pellet was injection molded to prepare a test piece. The evaluation results are shown in Table 3.

Example 18 Polycarbonate resin (Lexan SP (trademark): terminal hydroxyl group ratio 10%, Nippon GE Plastics Co., Ltd.)
9 kg, polybutylene terephthalate resin (Barox (trademark): Japan GE Plastics Co., Ltd.) 1
kg, ECR glass fiber (Asahi Fiber Glass Co., Ltd.)
1 kg, tetramethylammonium hydroxide (Me ₄ NO
H) 0.45 g and oxalic acid ((COOH) ₂ ) 0.45 g were pelletized in an extruder. This pellet was injection molded to prepare a test piece. The results of these evaluations are shown in Table 3.

[0095]

[Table 3]

Comparative Example 1 Polycarbonate resin (Lexan (trademark): terminal hydroxyl group ratio 10%, manufactured by GE Plastics Co., Ltd.) 9
kg, polybutylene terephthalate resin (Barox ™: Japan GE Plastics Co., Ltd.) 1 kg, and ECR glass fiber (Asahi Fiber Glass Co., Ltd.) 1
kg was pelletized in the extruder. This pellet was injection molded to prepare a test piece. Table 1 shows the evaluation results.

Comparative Example 2 Polycarbonate resin (Lexan (trademark): 10% of terminal hydroxyl group, manufactured by GE Plastics Co., Ltd.) 7
kg, polybutylene terephthalate resin (Barox ™: Japan GE Plastics Co., Ltd.) 3 kg, and ECR glass fiber (Asahi Fiber Glass Co., Ltd.) 1
kg was pelletized in the extruder. This pellet was injection molded to prepare a test piece. Table 1 shows the evaluation results.

Comparative Example 3 A test piece was prepared in the same manner as in Comparative Example 1 except that glass fiber having a refractive index of 1.545 was used instead of ECR glass fiber having a refractive index of 1.579. The evaluation results are shown in Table 1 together with the blending amount.

Comparative Example 4 A test piece was prepared in the same manner as in Comparative Example 1 except that 0.45 g of tetramethylammonium hydroxide and 2.7 g of phosphorous acid were added to the compounding of Comparative Example 2 in the compounding disposal of Comparative Example 3. did. The evaluation results are shown in Table 1 together with the blending amount.

Comparative Example 5 Polycarbonate resin (Lexan (registered trademark): 0% terminal hydroxyl ratio, manufactured by GE Plastics Co., Ltd.) 6 kg, polybutylene terephthalate resin (Barox (registered trademark),
Japan GE Plus Chix Co., Ltd.) 4kg and EC
1 kg of R glass fiber (manufactured by Asahi Fiber Glass Co., Ltd.) was pelletized by an extruder. This pellet was injection molded to prepare a test piece. Table 1 shows the evaluation results.

Comparative Example 6 A test piece was prepared in the same manner as in Example 9 except that glass fiber having a refractive index of 1.545 was used instead of ECR glass fiber having a refractive index of 1.579. The evaluation results are shown in Table 2 together with the blending amount.

Comparative Example 7 Polycarbonate resin (Lexan (trademark): 35% of terminal hydroxyl group, manufactured by GE Plastics Co., Ltd.) 7 kg,
Kodar A150 (Trademark: Eastman Kodak Company)
3 kg and 1 kg of ECR glass fiber (manufactured by Asahi Fiber Glass Co., Ltd.) were pelletized by an extruder. This pellet was injection molded to prepare a test piece. The evaluation results are shown in Table 3.

Comparative Example 8 Polycarbonate resin (Lexan (trademark): 35% of terminal hydroxyl groups, manufactured by GE Plastics Corporation) 8 kg,
2 kg of polycyclohexanedimethanol terephthalate (synthetic product) and 1 kg of ECR glass fiber (manufactured by Asahi Fiber Glass Co., Ltd.) were pelletized by an extruder. This pellet was injection molded to prepare a test piece. The evaluation results are shown in Table 3.

Comparative Example 9 Polycarbonate resin (Lexan (trademark): 35% of terminal hydroxyl group, manufactured by GE Plastics Co., Ltd.) 6 kg,
4 kg of polycyclohexanedimethanol terephthalate (synthetic product) and 1 kg of ECR glass fiber (manufactured by Asahi Fiber Glass Co., Ltd.) were pelletized with an extruder. This pellet was injection molded to prepare a test piece. The evaluation results are shown in Table 3.

Comparative Example 10 Polycarbonate resin (Lexan (trademark): 35% of terminal hydroxyl groups, manufactured by GE Plastics Corporation) 9 kg,
1 kg of polyethylene terephthalate resin (Mitsui PET (trademark), manufactured by Mitsui Petrochemical Co., Ltd.) and 1 kg of ECR glass fiber (manufactured by Asahi Fiber Glass Co., Ltd.) were pelletized by an extruder. This pellet was injection molded to prepare a test piece. The evaluation results are shown in Table 3.

Comparative Example 11 Polycarbonate resin (Lexan SP (trademark): 10% of terminal hydroxyl groups, manufactured by Nippon Di-Plastix Co., Ltd.) 9
kg, polybutylene terephthalate resin (Barox ™, Japan GE Plastics Co., Ltd.) 1 kg, and ECR glass fiber (Asahi Fiber Glass Co., Ltd.) 1
kg was pelletized in the extruder. This pellet was injection molded to prepare a test piece. The evaluation results are shown in Table 3.

[0107]

As is clear from Tables 1, 2, and 3 and the related description, by adding a polycarbonate resin having a terminal hydroxyl group, a catalyst, an acidic compound, and a phenolic compound, the difference in refractive index is 0.01 or less. (Haze and light transmittance) of resin composition containing glass
A glass-reinforced transparent resin composition having a significantly improved value was obtained.

Claims (11)

[Claims] 1. A) a-1) polycarbonate resin and / or a-2) polyester carbonate resin, and B) polyester resin, based on 100 parts by weight in total, C) the resin of component A). Blending 5 to 150 parts by weight of a glass filler having a difference in refractive index of 0.01 or less and 0.000005 to 0.5 parts by weight of D) a Lewis acid compound catalyst excluding a basic compound catalyst and / or a protonic acid. A transparent glass-reinforced resin composition comprising: 2. A) a-1) a polycarbonate resin and / or a-2) a polyester carbonate resin, and B) a total of 100 parts by weight of a polyester resin, and C) a refractive index with the resin of the component A). 5 to 150 parts by weight of a glass filler having a difference of 0.01 or less, and further E) a proton and / or its derivative 0.00000
A transparent glass-reinforced resin composition, characterized in that 1 to 1 part by weight is blended. 3. A) a-1) a polycarbonate resin and / or a-2) a polyester carbonate resin, and B) a total of 100 parts by weight of a polyester resin, and C) a refractive index with the resin of component A). 5 to 150 parts by weight of a glass filler having a difference of 0.01 or less, and further F) a compound having two or more phenolic hydroxyl groups 0.0
A transparent glass-reinforced resin composition, characterized by being blended with 01 to 5 parts by weight. 4. A glass having a refractive index difference of 0.01 or less with respect to C) the resin of component A), based on 100 parts by weight of A) polycarbonate resin and / or polyester carbonate resin and B) polyester resin in total. 5 to 150 parts by weight of filler, D) 0.000005 to 0.5 parts by weight of Lewis acidic compound catalyst excluding basic compound catalyst and / or protic acid, and E) 0.0000 of protic acid and / or its derivative
01 to 1 part by weight, and F) a compound having two or more phenolic hydroxyl groups 0.0
01 to 5 parts by weight, and at least two or more of the respective components D), E), and F) are combined and contained.
Transparent glass reinforced resin composition. 5. The component A) a-1) is a polycarbonate resin in which the proportion of terminal hydroxyl groups of the resin is 5 to 100% of all terminals. The transparent glass-reinforced resin composition described in 1. 6. A polycarbonate resin in which the proportion of terminal hydroxyl groups of the resin of component A) a-1) is from 10 to 100% of all terminals, wherein the resin is a polycarbonate resin. The transparent glass-reinforced resin composition of. 7. The polycarbonate resin in which the proportion of terminal hydroxyl groups of the resin of component A) a-1) is 20 to 100% of all terminals, 7. The transparent glass-reinforced resin composition of. 8. The respective composition ratios of the resin of the component A) and the resin of the component B) are 99 to 10 parts by weight for the component A) and 1 to 90 parts by weight for the component B). The transparent glass-reinforced resin composition according to any one of claims 1 to 7. 9. The respective composition ratios of the resin of the component A) and the resin of the component B) are 79 to 20 parts by weight for the component A) and 21 to 80 parts by weight for the component B). The transparent glass-reinforced resin composition according to any one of claims 1 to 7. 10. The composition ratio of the resin of the component A) to the resin of the component B) is 66 to 20 parts by weight for the component A) and 34 to 80 parts by weight for the component B). The transparent glass-reinforced resin composition according to any one of claims 1 to 7. 11. The resin of component B) is selected from the group consisting of polyethylene terephthalate, polybutylene terephthalate, cyclohexanedimethanol terephthalate, copolyesters of cyclohexanedimethanol and terephthalic acid / isophthalic acid, polyethylene naphthalate, polybutylene naphthalate. The transparent glass-reinforced resin composition according to any one of claims 1 to 10, wherein the polyester selected from the group consisting of a single type or a combination of two or more types.