JPH06116408A - Reinforced thermoplastic polyester sheet - Google Patents

Abstract

PURPOSE:To obtain a reinforced sheet excellent in soldering heat resistance, thermal stability, mechanical properties, processability, surface appearance, etc., by blending a polycyclohexanedimethylene terephthalate polyester resin with a filler, a crystallization promoter and an antioxidant, and forming the resulting mixture into a sheet. CONSTITUTION:50-95wt.% polycyclohexanedimethylene terephthalate polyester resin having an intrinsic viscosity of 0.5 to 2.0 and comprising 80% recurring units of the terephthalic acid residue and the 1,4-cyclohexanedimethanol residue bonded to each other is blended with 5-50wt.% fibrous filler and/or platy filler, and 0-10wt.% crystallization promoter such as talc, clay, calcium carbonate or a mixture thereof to prepare 100 pts.wt. compsn., which is then admixed with 0.05-5 pts.wt. at least one antioxidant selected from among hindered phenol compds. sulfur compds., phosphorus compds., etc. The resulting mixture is formed into a sheet.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a reinforced sheet, which is preferably used for a printed circuit board or the like, and which is formed by molding a mixture of a reinforced polycyclohexanedimethylene terephthalate polyester resin and at least one antioxidant.

[0002]

2. Description of the Related Art Polycyclohexane dimethylene terephthalate (hereinafter abbreviated as PCT) has excellent mechanical properties and chemical resistance, and is heat-deformed as compared with conventional polyesters such as polybutylene terephthalate and polyethylene terephthalate. Since the temperature is high, it is expected to be applied to applications such as electric / electronic device parts, automobile parts and mechanical parts, which are required to have heat resistance in recent years. However, PCT has a problem that it is easily affected by oxidative deterioration, and mechanical properties are deteriorated as the degree of polymerization is decreased. Therefore, the addition of various stabilizers has been studied for the purpose of preventing these deterioration phenomena.

According to Japanese Patent Publication No. 2-500033, PC
Hindered phenolic compounds, sulfur compounds,
Attempts are being made to improve the thermal stability by adding a phosphorus compound. However, the composition described in the same certificate has a problem that it cannot meet the requirements for heat resistance and mechanical properties, which have become severer in recent years.

JP-A-63-221159 attempts to improve the melt stability by adding an epoxy compound to the reinforced PCT. However, since an epoxy compound is used, if the amount added is too high, the viscosity becomes too high.

[0005]

The present invention solves the above-mentioned problems of the prior art, has high thermal stability, and is excellent in solder heat resistance, heat resistance, mechanical properties, workability, surface appearance and the like. An object is to provide a plastic polyester reinforced sheet.

[0006]

In order to solve the above problems, the present invention has the following constitution.

(A) A repeating unit in which a terephthalic acid residue and a 1,4-cyclohexanedimethanol residue are combined accounts for 80 mol% or more of the polymer and has an intrinsic viscosity of 0.5 to
Polycyclohexane dimethylene terephthalate-based polyester resin of 2.0 to 50 to 95% by weight and (B)
5 to 50% by weight of a filler (a) a fibrous filler and / or (b) a flat filler and (C) a crystallization accelerator 0 selected from talc, clay, calcium carbonate or a mixture thereof. 10% by weight, (A),
Oxidation consisting of one or more compounds selected from the group consisting of (D) hindered phenol compounds, sulfur compounds and phosphorus compounds, relative to 100 parts by weight of the total amount of (B) and (C). It is a thermoplastic polyester reinforced sheet obtained by sheet-forming a mixture containing 0.05 to 5 parts by weight of an inhibitor.

The present invention will be specifically described below.

The method for producing the (A) polycyclohexanedimethylene terephthalate polyester in the present invention is not particularly limited, but for example, in the presence or absence of a catalyst such as an organic titanium compound, terephthalic acid or its lower A method obtained by polycondensing an alkyl ester and 1,4-cyclohexanedimethanol can be mentioned. Polymerization conditions include, for example, US Pat.
The conditions and the like described in the specification of No. 1,466 can be applied.

(A) Isophthalic acid, orthophthalic acid, 2,6-naphthalenedicarboxylic acid, 2 or 6 in the range of 20 mol% or less, preferably 10 mol% or less of the acid component or diol component of the polycyclohexanedimethylene terephthalate polyester. , 7-naphthalenedicarboxylic acid,
1,5-naphthalenedicarboxylic acid, methylterephthalic acid, 4,4'-biphenyldicarboxylic acid, 2,2'-biphenyldicarboxylic acid, 1,2-bis (4-carboxyphenoxy) -ethane, succinic acid, adipic acid , Suberic acid, azelaic acid, sebacic acid, dodecanedioic acid, octadecanedicarboxylic acid, dimer acid and other dicarboxylic acids such as 1,4-cyclohexanedicarboxylic acid or ethylene glycol, propylene glycol, 1,5
-Pentanediol, 1,6-hexanediol, 1,
8-octanediol, 1,10-decanediol,
Substitutions with other diols such as 1,3-cyclohexanedimethanol, 1,2-cyclohexanedimethanol and 2,2-bis (2'-hydroxyethoxyphenyl) propane can also be used.

(A) 1,4-Polycyclohexanedimethylene terephthalate polyester used in the present invention
The cyclohexane ring that is a part of the cyclohexanedimethanol residue preferably has a cis / trans ratio (molar ratio), which is the ratio of the cis structure and the trans structure, in the range of 60/40 to 10/90, and more preferably. 50/50 ~
15/85, more preferably 40/60 to 25/75
Is the range. When the cis / trans ratio is 60/40 or more, the melting point of the polyester becomes low, which makes it difficult to apply it to applications requiring heat resistance.
When it is less than 0, the melting point of the polyester becomes too high, and the difference between the decomposition temperature and the molding temperature becomes small, and it becomes difficult to improve the thermal stability during molding even with the technique of the present invention.

The (A) polycyclohexane dimethylene terephthalate polyester used in the present invention has an intrinsic viscosity of 0.5 to 2.0 dl / g when measured at 25 ° C. using o-chlorophenol as a solvent, It is preferably 0.5 to 1.0 dl / g.

(A) Polycyclohexanedimethylene terephthalate polyester has an intrinsic viscosity of 0.5 dl / g
Less than 2.0, the mechanical properties are low, while 2.0 dl / g
If it exceeds, the moldability tends to be poor.

The amount of terminal carboxyl groups of the (A) polycyclohexanedimethylene terephthalate polyester is 100 equivalents or less of 10 ⁶ g-polymer, preferably 30 equivalents or less of 10 ⁶ g-polymer, more preferably 1 or less.
It is desirable that it is 5 equivalents or less than 10 ⁶ g-polymer.

The amount of terminal carboxyl groups of the (A) polycyclohexanedimethylene terephthalate polyester is
For example, Anal. Chem. , 26.1614-161
6 (1954). A. It can be measured using the method of Pohl.

Typical examples of the (a) fibrous filler constituting the (B) filler used in the present invention include glass fiber, carbon fiber, metal fiber, ceramic fiber, asbestos, needle-like wallastonite and rock wool. , Whiskers such as slag wool and potassium titanate, and these can be used in combination of two or more kinds. Further, among these fibrous fillers, glass fiber is particularly suitable.

(A) The fiber diameter of the fibrous filler is 2 to 20 μm.
m is preferable, and particularly preferably 3 to 15 μm. The average length of the fibrous filler dispersed in the polymer is preferably about 0.05 to 1 mm, and particularly preferably 0.1 to 0.5 mm.

(B) Examples of the flat filler include mica (muscovite, biotite, phlogopite, synthetic mica), glass flakes, sericite, alumina, and the like, and these may be used in combination of two or more kinds. . Among these flat fillers, mica is particularly preferable.

(B) The average particle size of the flat filler is 1 to 1500 μm, preferably 2 to 1000 μm, more preferably 4 to 700 from the viewpoint of melt fluidity and sheet surface appearance.
Those having a thickness of μm are preferably used. Here, the average particle size is J
It is a value shown with a particle size corresponding to 50% by weight of the cumulative weight of the particle size distribution measured by the coarse sieving method described in IS K-5101.

The ratio of (a) the fibrous filler to (b) the flat filler is the ratio of the fibrous filler / the flat filler (weight ratio) in terms of the effect of suppressing anisotropy, the processability and the appearance of the sheet surface. Is 90 /
It is preferably in the range of 10 to 30/70, more preferably 85/15 to 35/65, and further preferably 7
It is in the range of 5/25 to 45/55.

Examples of the (C) crystallization accelerator used in the present invention include talc, clay and calcium carbonate, and these may be used in combination of two or more kinds. Further, talc is particularly preferable.

(A) Polycyclohexane dimethylene terephthalate type polyester resin in the present invention, (B)
The blending ratio of the filler and the (C) crystallization accelerator is 50 to 95% by weight of the component (A), preferably 60 to 90% by weight,
The component (B) is 5 to 50% by weight, preferably 10 to 40% by weight, and the component (C) is 0 to 10% by weight, preferably 0 to 5% by weight. (B) Heat resistance when the filler is less than 10% by weight,
Mechanical properties are low and not preferable. On the other hand, (B) filler is 5
If it exceeds 0% by weight, fluidity and sheet surface appearance are deteriorated, which is not preferable.

The antioxidant (D) used in the present invention is one or two selected from the group consisting of hindered phenol compounds, sulfur compounds and phosphorus compounds.
Composed of more than one compound.

As the hindered phenolic compound,
Tris (β- (3,5-di-t-butyl-4-hydroxy-phenyl) propionyl-oxyethyl) isocyanurate, 2,4-di-t-butyl-phenyl-3,5
-Di-t-butyl-4-hydroxybenzoate, 1,
1,3-tris (2-methyl-4-hydroxy-5-t
-Butyl-phenyl) butane, 2,2'-methylene-bis (4-methyl-6-butyl-phenol), 1,3,5
-Tris (3,5-di-t-butyl-4-hydroxypentyl) isocyanurate, tetrakis (methylene-3)
-(3 ', 5'-di-t-butyl-4'-hydroxyphenyl) propionate) methane, 2,2-thio- (dimethyl-bis-3 (3,5-di-t-butyl-4-hydroxy) Phenol) propionate), n-octadecyl-
3- (4'-hydroxy-3 ', 5'-butylphenol) propionate, N, N'-hexamethylene-bis (3,5
-Di-t-butyl-4-hydroxy-hydrocinamide, nickel salt of bis (3,5-di-t-butyl-4-hydroxypentylphosphoric acid) monomethyl ester, 1,3,5-tri- Methyl-2,4,6-tris (3,5-di-t-butyl-4-hydroxy-benzyl) benzene, tetrakis (methylene-3- (3 ', 5')
-Di-t-butyl-4'-hydroxyphenyl) propionate) methane, 1,3,5-tris (3,5-di-t
-Butyl-4-hydroxy-benzyl) benzene and the like can be preferably used. These may be used alone or in the form of ester.

Specific examples of the sulfur compounds include the following. Di-n-hexyl ralphide, distearyl sulfide, dipentyl sulfide, diphenyl sulfide, dioctyl thiodipropionate, dilauryl thiodipropionate, thiodiethanol dilaurate, bis (dodecylthio) methane, 1,1-bis (stearyl) Thio) ethane, dodecyl mercaptan, thioglycolic acid lauryl ester, 3-mercaptopropionic acid stearyl ester, 3-mercaptopropionic acid pentyl ester, 4-mercaptobutyric acid lauryl ester, 6-mercaptocaproic acid stearyl ester, mercaptopropionic acid ethylene glycol Ester, thioglycolic acid penzoquinone ester, glycerin tris (6-mercaptocaproic acid) ester, N-
Stearyl-mercaptoglycolic acid amide, thioglycolic acid anilide, N-lauryl-4-mercaptobutyric acid amide, 6-mercaptocaproic acid anilide, N, N'-
Bis (3-mercaptopropionyl) xylylenediamine.

Examples of phosphorus compounds include phosphoric acid, dimethyl phosphate, trimethyl phosphate, trimethyl phosphate, methyl diethyl phosphate, triethyl phosphate, triisophosphate, tributyl phosphate, triphenyl phosphate, tribenzyl phosphate. , Tricyclohexyl phosphate,
Triphenyl phosphite, diphenyl phosphite, tristearyl phosphite, diphenylisooctyl phosphite, tris-noelphenyl phosphite, bis (2,4-di-t-butylphenyl) pentaerythritol-diphosphite, bis (2,2 6-di-t-butyl-4-methylphenyl) pentaerythritol-diphosphite, bis (2,4-di-t-butylphenyl) pentaerythritol-diphosphite, distearyl pentaerythritol-diphosphite, tris (2,4
-Di-t-butylphenyl) phosphite and the like.

(D) The amount of antioxidant added is (A),
0.05 to 100 parts by weight of the total amount of (B) and (C)
It is 5 parts by weight, preferably 0.1 to 3 parts by weight, and more preferably 0.2 to 2 parts by weight. If the amount added is less than 0.05 parts by weight, it is difficult to maintain sufficient thermal stability. On the other hand, if the amount exceeds 5 parts by weight, the whole molecular weight decreases,
It is not preferable because it causes deterioration of mechanical properties and the like.

Further, the thermoplastic polyester reinforced sheet of the present invention comprises a heat stabilizer, an ultraviolet absorber, a light stabilizer, a lubricant, a plasticizer, an antistatic agent, a dye and a pigment, etc. within a range not impairing the object of the present invention. One or more additives may be contained.

In producing the thermoplastic polyester reinforced sheet of the present invention, a sheet forming method known to those skilled in the art can be adopted. Generally, the composition is pre-pelletized to
A desired sheet is obtained from a die-attached sheet extruder through a polishing roll or a casting roll.

The thermoplastic polyester reinforced sheet of the present invention has excellent mechanical properties, solder heat resistance and heat resistance, and is used for household appliances, sports equipment parts, electric / electronic industrial parts and electric insulators, It can be used for various purposes such as automobile parts and circuit boards.

[0031]

The present invention will be described in more detail with reference to the following examples.
All parts and% in the examples are based on weight.

Reference Example (1) Preparation of Polycyclohexanedimethylene terephthalate type polyester resin A-1: "EKTER" 6 manufactured by Eastman Kodak Company
761 was used.

A-2: "E" manufactured by Eastman Kodak Company
KTER "3879 was used.

(2) Preparation of Filler B-1: Glass fiber having a fiber diameter of 13 μm and a fiber length of 3 mm (3PE-941S manufactured by Nitto Boseki Co., Ltd.) was used.

B-2: White mica having an average particle size of 24 μm (“Micalet 51P” manufactured by Yamaguchi Mica Industry Co., Ltd.) was used.

(3) Preparation of Crystallization Accelerator C-1: Talc (Takehara Chemical Industry Co., Ltd. US-150)
S) was used.

(4) Preparation of antioxidant D-1: tetrakis (methylene-3- (3 ', 5'-di-t
-Butyl-4'-hydroxyphenyl) propionate)
Methane ("Irganox" manufactured by Nippon Ciba Geigy)
1010) was used.

D-2: Bis (2,6-di-t-butyl-)
4-Methylphenyl) pentaerythritol-diphosphite (PEP36 manufactured by Asahi Denka Co., Ltd.) was used.

D-3: Dilauryl thiodipropionate ("Rasmit" manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.) was used.

D-4: tris (4-glycidyloxyphenyl) methane (XD-9053.0 manufactured by Dow Chemical Co.)
1) was used.

Examples 1 to 7 (A) Polycyclohexanedimethylene terephthalate polyester resin prepared in Reference Example, (B) Filler,
(C) Crystallization accelerator and (D) Antioxidant were mixed in the compounding ratio shown in Table 1, and melt-kneaded and extruded at a resin temperature of 300 ° C. with a vented 40 mmφ extruder to produce pellets.

Then, using a sheet forming machine (sheet extrusion temperature 300 ° C.) equipped with three vertical polishing rolls, the thickness is 1 mm.
The sheet was processed into a sheet, and a test piece obtained by a punching press was evaluated. The evaluation method was as follows.

A. Tensile strength: According to ASTM D-638.

B. Melt index (MI): 300
It was measured at a temperature of 1 ° C. and a load of 1 kg. Other conditions are ASTM
According to D-1238.

C. Solder heat resistance: A test piece processed to a size of 20 × 60 × 1 (mm) was immersed in a solder bath at 260 ° C., and changes in appearance such as foaming and discoloration were visually observed. The immersion time was 20 sec and 60 sec.

Comparative Examples 1 to 7 (A) Polycyclohexanedimethylene terephthalate polyester resin prepared in Reference Example, (B) Filler,
The crystallization accelerator (C) and the antioxidant (D) were mixed at the compounding ratios shown in Table 1, and test pieces were prepared and evaluated in the same manner as in the examples. The evaluation results are shown in Table 1.

[0047]

[Table 1] The following is clear from the examples and comparative examples.

That is, all of the thermoplastic polyester reinforced sheets obtained by the present invention are excellent in mechanical strength, thermal stability and solder heat resistance.

On the other hand, the thermoplastic polyester reinforced sheet having a small amount of the filler (B) (Comparative Example 1) is inferior in mechanical strength and solder heat resistance, and conversely, the thermoplastic polyester reinforced sheet (Comparative Example 2) is too large. Since the fluidity deteriorates, the surface appearance deteriorates, and the mechanical strength also deteriorates, which is not preferable. Further, the thermoplastic polyester-reinforced sheets (Comparative Examples 3 and 4) to which the antioxidant (D) is not added or whose amount is small are inferior in thermal stability due to a decrease in viscosity, and conversely, when too much (comparative) Example 5) is not preferable because it causes a decrease in viscosity and a decrease in mechanical strength. When the epoxy compound is used as the antioxidant, the effect is not exhibited when the addition amount is small (Comparative Example 6), and conversely, when the addition amount is large (Comparative Example 7), the viscosity is increased and a sample cannot be obtained. There is.

[0050]

According to the present invention, it is possible to provide a thermoplastic polyester reinforced sheet which has high thermal stability and is excellent in solder heat resistance, heat resistance, mechanical properties, workability, surface appearance and the like.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁵ Identification code Internal reference number FI Technical display location C08K 5/51 KKD 7242-4J 7/02 C08L 67/02 KKF 8933-4J

Claims (2)

[Claims] 1. A repeating unit in which (A) a terephthalic acid residue and a 1,4-cyclohexanedimethanol residue are combined occupies 80 mol% or more of the polymer and has an intrinsic viscosity of 0.5 to 0.5.
Polycyclohexane dimethylene terephthalate-based polyester resin of 2.0 to 50 to 95% by weight and (B)
5 to 50% by weight of a filler (a) a fibrous filler and / or (b) a flat filler and (C) a crystallization accelerator 0 selected from talc, clay, calcium carbonate or a mixture thereof. 10% by weight, (A),
Oxidation consisting of one or more compounds selected from the group consisting of (D) hindered phenol compounds, sulfur compounds and phosphorus compounds, relative to 100 parts by weight of the total amount of (B) and (C). A thermoplastic polyester reinforced sheet formed by sheet-forming a mixture containing 0.05 to 5 parts by weight of an inhibitor. 2. A weight ratio of (a) fibrous filler / (b) flat filler in (B) filler is 90/10 to 30/7.
The thermoplastic polyester reinforced sheet according to claim 1, wherein the range is 0.