JPH02222447A - Thermoplastic resin composition - Google Patents

Abstract

PURPOSE:To obtain a composition which is excellent in shock resistance, heat resistance, mechanical strength, moldability and fluidity by adding a polycarbonate resin to a specific aromatic polyester-polyorganosiloxane block copolymer at a specific ratio. CONSTITUTION:(A) A polycarbonate resin having a recurring unit of formula I (R6, R7 are monovalent lower alkyl which may be substituted with halogens; E is hydrogen or the like) is mixed with an aromatic polyester- polyorganosiloxane block copolymer consisting of (B1) a polyester resulting from polycondensation reaction between an aromatic dicarboxylic acid and a diol and (B2) a polyorgano-siloxane of formula II (R1, R2 are methyl or the like; Q, Q' are divalent organic residue; n is 10 or more) at a weight ratio of 10/90 to 90/10 A/B.

Description

Detailed Description of the Invention (Field of Industrial Application) The present invention relates to a thermoplastic resin composition having excellent impact resistance, heat resistance, mechanical strength, moldability, fluidity, etc. The present invention relates to a thermoplastic resin composition composed of a specific aromatic polyester-polyorganosiloxane block copolymer.

(Prior art and problems to be solved) Polycarbonate resin has properties such as high impact strength, toughness, high transparency, good dimensional stability, good cleaving resistance, and good flame retardancy, and is an excellent It is known as a molding material. However, the impact strength of polycarbonate depends on its thickness, and the impact strength of thick molded products is extremely low.Furthermore, glass fiber is often used as a filler in polycarbonate resin; Adversely affects the impact properties of polycarbonate resin.

The present invention aims to improve the impact resistance of thick molded products and molded products containing glass fiber fillers while maintaining the original excellent performance of polycarbonate resins.

(Means for Solving the Problems) In order to achieve the above-mentioned objects, the inventors of the present invention, as a result of extensive studies, have combined polycarbonate resin with an aromatic polyester-polyorganosiloxane block copolymer. The present invention was achieved by discovering that the blended resin composition has significantly improved impact resistance and is also excellent in heat resistance, mechanical strength, moldability, and fluidity.

Namely, the thermoplastic resin composition of the present invention consists of a polycarbonate resin (A) and an aromatic polyester-polyorganosiloxane block copolymer (B), and the weight ratio of A to B (A/B) is to /90 to 90/10.

In the composition of the present invention, the weight ratio of the two components, that is, A/B, is 1G/90 to 90/10, but if it deviates from this range, the heat resistance and ** resistance, which are the characteristics of the composition of the present invention, This is not preferable because it damages the

The polycarbonate resin (A) used in the present invention has the following formula: represents a group, E represents a group or atom selected from the group consisting of hydrogen, lower alkyl group, halogen, and mixtures thereof, and has a repeating unit represented by ), which may be the same or different; Obtained by reacting phenol with a carbonate precursor.

Examples of this diphenol include 2,2-bis(4-hydroxyphenyl)propane, bis(4-hydroxyphenyl)methane, 2,2-bis(4-hydroxy-3-methylphenyl)propane, and 4,4-bis(4-hydroxyphenyl)propane. (4-hydroxyphenyl)hebutane, 2.2-(3,5,3',5
'-Tetrachlor-4,4'-dihydroxydiphenyl)propane, 2°2-(3,5,3',5'-tetrabromo-4,4'-dihydroxydiphenyl)propane, (3,3'-dichloro-4 , 4'-dihydroxydiphenyl)methane and the like.

These can be used alone or in combination of two or more. Preferably it is 2,2-bis(4-hydroxyphenyl)propane.

Further, the carbonate precursor described above can be any of carbonyl halide, carbonate ester, or haloformate. Carbonyl halides are carbonyl bromide, carbonyl chloride, and mixtures thereof. Carbonate esters include diphenyl carbonate, di(chlorphenyl) carbonate, di(
Bromphenyl) carbonate, di(trichlorophenyl) carbonate, di(tribromphenyl) carbonate, di(tolyl) carbonate, di(naphthyl) carbonate, dichloro(naphthyl) carbonate, phenyltricarbonate, chlorphenylchlornaphthyl carbonate, etc. listed, and these alone:
Alternatively, two or more types can be used in combination. Carbonyl chloride is preferred.

Next, the aromatic polyester-polyorganosiloxane block copolymer (B) used in the present invention will be explained.

This aromatic polyester-polyorganosiloxane block copolymer (B) is a block copolymer of aromatic polyester and polyorganosiloxane, and has aromatic polyester units and polyorganosiloxane units. However, the composition ratio of aromatic polyester and polyorganosiloxane is preferably 90:10 to 10:90 in terms of weight ratio.

One polyester segment has a number average molecular weight of 180
It is preferable that the polyorganosiloxane segment has a number average molecular weight of 0 or more, and it is preferable that one polyorganosiloxane segment has a number average molecular weight of 700 or more.If it is less than this, the elasticity tends to decrease, and as a result, the physical properties of the composition are deteriorated. Undesirable.

The aromatic polyester of the above-mentioned aromatic polyester-polyorganosiloxane block copolymer (B) is selected from (a) aromatic radicals, bonic acids, dihydric phenols, lower aliphatic diols, and alicyclic diols. Polyester made by condensation polymerization with one or more selected diols.

(b), a polyester formed by condensation polymerization of an aromatic hydroxycarboxylic acid; or

(C), a polyester copolymer consisting of (a) and (b), is the main component.

The aromatic carboxylic acid in (a) above has the following formula: [wherein R1 is a substituted or unsubstituted phenylene group, -CH,
- or -CO-) or a naphthylene group] Here, examples of the substituent of the phenylene group include chlorine, bromine, and a methyl group.

Substituted phenylene groups may be substituted with 1 to 4 substituents.

As the aromatic dicarboxylic acid represented by the above formula.

For example, terephthalic acid, isophthalic acid, diphenyl-m,
vs'-dicarboxylic acid, diphenyl-p, p'-dicarboxylic acid, diphenylmethane 1. -'-dicarboxylic acid, diphenylmethane-p,p'-dicarboxylic acid, benzophenone-4,4'-dicarboxylic acid, naphthalene dicarboxylic acid, etc., but these may be used alone or in combination of two or more. Can be done. Also, adipic acid,
There is no problem even if a small amount of aliphatic dicarboxylic acid such as sebacic acid is used.

Examples of the dihydric phenol in (a) include hydroquinone, resorcinol, dihydroxynaphthalene, biphenol (biphenyldiol), 1,8-dihydroxyanthraquinone, and the following formula: (wherein, R4 is an oxygen atom, a sulfur atom, -CO--SO, - or an alkylene group having 5 or less carbon atoms which may be substituted with halogen), such as 2,2-bis(4-hydroxyphenyl)propane (bisphenol A) , 4.4'-dihydroxydiphenylsulfone,
4,4'-dihydroxydiphenyl ether, 4.4'
-diphenyl sulfide, 4,4'-dihydroxydiphenyl ketone.

4.4'-dihydroxydiphenylmethane, 1,1-bis(4-hydroxyphenyl)-ethane, 1,1'-bis(4-hydroxyphenyl)-butane, 1,1-bis(4-hydroxyphenyl)-2 , 2,2-trichloro-ethane, etc., and these may be used alone or in combination of two or more.

The lower aliphatic diol in the above (,) is an alkylene diol having 2 to 6 carbon atoms, for example.

Ethylene glycol, propylene glycol, 1.4-
Butanediol, 1,5-bentanediol, 1,6-
Examples include hexanediol, which can be used alone or with 2
You may use a mixture of more than one species.

Further, examples of the alicyclic diol in (a) include cyclohexanediol, cyclohexane dimetatool, and the like. These may be used alone or in combination of two or more.

The aromatic hydroxycarboxylic acid used in (b) above represents a group represented by the following formula: % (wherein, X represents a direct bond or an alkylene group having 5 or less carbon atoms) or a naphthylene group] It is indicated by.

Such aromatic hydroxycarboxylic acids include 1-hydroxybenzoic acid, P-hydroxybenzoic acid, 1-hydroxy-6-naphthoic acid, 2-(4'-hydroxyphenyl)-2-(4'- (carboxylphenyl)-propane, 4-hydroxyphenyl-4-carboxylphenyl ether, etc., and these may be used alone or in combination of two or more.

Preferred polyester segments of the aromatic polyester-polyorganosiloxane block copolymer (B) of the present invention include an aromatic polyester consisting of terephthalic acid and 1,4-butanediol, a mixture of terephthalic acid and isophthalic acid, and a mixture of terephthalic acid and isophthalic acid. .2-bis(4-hydroxyphenyl)propane, an aromatic polyester consisting of
Copolymer of P-hydroxybenzoic acid, 2,6-naphthalene dicarboxylic acid and hydroquinone, copolymer of P-hydroxybenzoic acid, 2,6-naphthalene dicarboxylic acid, isophthalic acid and hydroquinone, P-hydroxybenzoic acid and 6
- Copolymer of hydroxy-2-naphthoic acid, P-hydroxybenzoic acid, 2,6-naphthalene dicarboxylic acid and 2,
Examples include copolymers of 6-naphthalenediol.

Also.

The aromatic polyester used for the polyester segment may be a polyester exhibiting liquid crystallinity.

In addition, the preferred polyorganosiloxane of the aromatic polyester-polyorganosiloxane block copolymer (B) of the present invention has the following formula: represents a divalent organic group, and Q and Q' represent a divalent organic group.

n represents an integer of 10 or more), preferably the following formula: (In the formula, R, , R, each independently represents a methyl group or a phenyl group, and R6 is a lower alkylene group or a lower alkylene ether group. (where n represents an integer of 10 or more). More preferred is polydimethylsiloxane.

The aromatic polyester-polyorganosiloxane block copolymer (B) used in the present invention can be prepared by known melt condensation polymerization, solution condensation polymerization,
It can be produced by methods such as interfacial condensation polymerization.

For example, for terminal alkylamine type polyorganosiloxane and aromatic polyester, AC5゜poly
m, prop (1983) and 30th Nationa
l SAMPE Symposium March 1
9-21.1985. In addition, the terminal dimethylamine type polyorganosiloxane and aromatic polyester are Ind, Eng, Che
m,Prod,Res,Davelop,,Vol,1
2. No, 41973 and TItANSACTIONS
OF TIIE 5OCIETY OF RHEOLO
GY 21:2,273-290 and Applied P.
olymer Symposiu+s No.

22, 143-156 (1973) and 30th Nat.
ional SAMPE Symposium Mar
It can be produced by the method described in ch 19-21.1985.

In addition, a method of reacting a terminal diol-type polyorganosiloxane, an aromatic dicarboxylic acid civalide, and a dihydric phenol in a halogenated organic solvent such as chloroform using a tertiary amine such as pyridine as a dehydrochlorination agent, and a method for forming an aromatic polyester In the presence of a transesterification catalyst, monomers or aromatic polyesters are transesterified with polyorganosiloxanes having amino groups at both ends.

It can be produced by melt condensation polymerization, and any method may be used.

The thermoplastic resin composition of the present invention can be prepared, for example, as follows using a polycarbonate resin (A) and an aromatic polyester-polyorganosiloxane block copolymer (B).

Components (A) and (B) are mechanically mixed in a predetermined ratio using a known device such as a panbali mixer or an extruder, and extruded into pellets.

At this time, in addition to components (A) and (B), stabilizers, plasticizers, lubricants, flame retardants, pigments, reinforcing fillers, etc. may be added as necessary.

Preferred embodiments of the present invention are as follows.

(1) Polycarbonate resin (A) has a linear formula: (wherein,
R, , R, each independently represent a monovalent lower alkyl group, an aryl group, and an alicyclic group which may be substituted with halogen, and E consists of hydrogen, a lower alkyl group, a halogen, and a mixture thereof. (represents a group or atom selected from a group)
A thermoplastic resin composition according to the claims, which has a repeating unit represented by:

(2) The thermoplastic resin composition according to item (1) above, wherein the polycarbonate resin (A) has a repeating unit represented by the following linear formula:

(3) The aromatic polyester-polyorganosiloxane block copolymer (B) contains (a) an aromatic dicarboxylic acid and one or more diols selected from dihydric phenols, lower aliphatic diols, and alicyclic diols. (b), a polyester formed by condensation polymerization of an aromatic hydroxycarboxylic acid, or (C), a polyester copolymer consisting of (a) and (b) as the main constituent components. polyester segment,
The following formula.

The aromatic dicarboxylic acid constituting Chil has the following formula: [wherein R
2 is a substituted or unsubstituted phenylene group.

represents a group represented by -CH2- or -CO-) or a nabutylene group] (In the formula, R,, R, each independently represent a methyl group or a phenyl group, and Q and Q' each independently represents a divalent organic group, and n represents an integer of 10 or more. Thermoplastic resin composition.

(4) In the aromatic polyester-polyorganosiloxane block copolymer (B), the aromatic polyvarnish (in the formula,
The thermoplastic resin composition according to item (3), wherein R4 represents an oxygen atom, a sulfur atom, -CO--SO, -, or an alkylene group having 5 or less carbon atoms which may be substituted with a halogen.

(5) In the aromatic polyester-polyorganosiloxane block copolymer (B), the aromatic dicarboxylic acid constituting the aromatic polyester is terephthalic acid and/or isophthalic acid, and the dihydric phenol is 2,2-bis(4
-hydroxyphenyl)propane, the thermoplastic resin composition according to item (4) above.

(6) The aromatic dicarboxylic acid constituting the aromatic polyester in the aromatic polyester-polyorganosiloxane block copolymer (B) is represented by the above formula 1, and
The lower aliphatic diol is an alkylene diol having 2 to 6 carbon atoms, and the alicyclic diol is an alicyclic diol.

The thermoplastic resin composition according to item (3) above, which is cyclohexanediol or cyclohexane dimetatool.

(7) In the aromatic polyester-polyorganosiloxane block copolymer (B), the aromatic dicarboxylic acid constituting the aromatic polyester is terephthalic acid and/or isophthalic acid, and the lower aliphatic or alicyclic diol is ethylene glycol. and the above (6) which is l or 1,4-butanediol and/or cyclohexane dimetatool.
The thermoplastic resin composition described in .

(8) In aromatic polyester-polyorganosiloxane block copolymer CB), the aromatic polyester is
The thermoplastic resin composition according to item (3) above, which is a polyester exhibiting liquid crystallinity.

(9) In the aromatic polyester-polyorganosiloxane block copolymer (B), the aromatic polyester is
The thermoplastic resin composition according to item (8) above, which is a copolymer of P-hydroxybenzoic acid, 2,6-naphthalene dicarboxylic acid, and hydroquinone.

(10) The aromatic polyester-polyorganosiloxane block copolymer (B) according to item (8), wherein the aromatic polyester is a copolymer of P-hydroxybenzoic acid and 6-hydroxy-2-naphthoic acid. Thermoplastic resin composition.

(11) The aromatic polyester in the aromatic polyester-polyorganosiloxane block copolymer (B) is a copolymer of P-hydroxybenzoic acid, 2,6-naphthalene dicarboxylic acid, and 2,6-naphthalene diol. The thermoplastic resin composition described in (8).

(12) In the aromatic polyester-polyorganosiloxane block copolymer (B), the aromatic polyester is a copolymer of P-hydroxybenzoic acid, 2,6-naphthalene dicarboxylic acid, hydroquinone, and isophthalic acid (8) above. The thermoplastic resin composition described in .

(13) In the aromatic polyester-polyorganosiloxane block copolymer (B), the polyorganosiloxane has the following formula: Among the methods, the Izod impact strength is determined by ASTM D256.
1 part 8 inch and 1 part 4 inch notched isot impact strength was measured at 23°C.

First, a synthesis example of the aromatic polyester-organosiloxane block copolymer (B) will be shown.

Synthesis Example 1 (wherein R1, R, each independently represents a methyl group or phenyl group, R5 represents a lower alkylene group or lower alkylene ether group, and n represents an integer of 10 or more) The thermoplastic resin composition described in (3).

(14) The thermoplastic resin composition according to item (13) above, wherein the polyorganosiloxane in the aromatic polyester-polyorganosiloxane block copolymer (B) is polydimethyloxane.

(Example) Hereinafter, the present invention will be explained in more detail with reference to Examples. In addition, 15 parts of polydimethylsiloxane (M, v2000), which is shown in the evaluation power of the composition used in the examples, and 5.5 parts each of terephthalic acid chloride and isophthalic acid chloride were charged into a reaction vessel equipped with a stirrer, and purified by distillation. A homogeneous solution was made with 200 parts of chloroform, and 9.6 parts of bisphenol A (a homogeneous solution was made with 50 parts of distilled chloroform and 10 parts of pyridine) was added under an ice bath N3, and the reaction solution was stirred for 6-8 hours. After washing with dilute hydrochloric acid and water, the polymer was reprecipitated with methanol to recover polymer (S-1).

Synthesis Example 2 3.9 parts of dimethyl terephthalate, 3.6 parts of 1,4-butanediol, and polydimethylsiloxane (Mjl1800) 4 represented by the following formula:
．． 4 parts were charged into a reaction vessel equipped with a stirrer, and further used as a catalyst.

50 ppm of a 1% butanol solution of butyl titanate [τ1(oc*nsL]) was added. The mixture was heated in a nitrogen atmosphere.

The temperature was raised from 150 to 250° C. over 4 hours while stirring, and then the pressure was gradually reduced to 250° C. to give 1 g of 0.5 mm over 2 hours. Furthermore, 250℃, 0.5mm
After stirring with Hg for 3 hours, the reaction was terminated and the polymer (S-2) was recovered.

Polydimethylsiloxane (M, 100) 15 shown in Synthesis Example 3
10.5 parts of P-acetoxybenzoic acid and 11.5 parts of 2-acetoxy-6-naphthoic acid were placed in a reaction vessel equipped with a stirrer, and as a catalyst, butyl titanate [Ti(Q
5 opp of a 1% butanol solution of C4H-)4] was added. This mixture was heated in a nitrogen atmosphere from 200 to 300°C over 3 hours while stirring.Then, the pressure was gradually reduced to 300°C to 0.5mm+Hg over 1 hour, and after stirring for 3 hours. , high viscosity polymer (S-3
) were collected.

Examples 1 to 9 Commercially available polycarbonate resin (A) (number average molecular weight 23
000) and the aromatic polyester-polyorganosiloxane block copolymer (B) obtained in Synthesis Examples 1 to 3 (S
-1 to 5-3) were mixed in an extruder with the composition shown in Table 1, and shaped into a pellet. The conditions were the same as usual. Furthermore, small berets were injection molded to the predetermined dimensions of each test piece. The Izot impact strength was measured using this, and the results are shown in Table 1.

Examples 10-12 Commercially available polycarbonate resin (A) (number average molecular weight 23
000), glass fibers and the aromatic polyester-polyorganosiloxane block copolymers (B) (S-1 to 5-3) obtained in Synthesis Examples 1 to 3 were used in the compositions shown in Table 1. In the same manner as in Example 1, test pieces were obtained by extrusion pelletizing and injection molding under the same conditions. Evaluation was carried out in the same manner as in Example 1, and the results are shown in Table 1.

Comparative Example 1 Commercially available polycarbonate resin (A) (number average molecular weight 23
000) was injection molded in the same manner as in Example 1 to obtain a test piece. Evaluation was conducted in the same manner, and the results are shown in Table 1.

Comparative Example 2 Commercially available polycarbonate resin (A) (number average molecular weight 23
000) and glass fibers having the compositions shown in Table 1 were extruded into pellets and then injection molded under the same conditions as in Example 1 to obtain test pieces. Evaluation was carried out in the same manner as in Example 1, and the results are shown in Table 1.

The following margin NB: Not destroyed (effect of the invention) According to the present invention, by combining and blending the aromatic polyester-polyorganosiloxane block copolymer with the polycarbonate resin, without impairing the original properties of the polycarbonate resin, In particular, when a thick molded article is made, or furthermore, when a glass fiber filler is added to the molded article, the impact resistance can be significantly improved.

Claims (1)

[Claims] (1) Polycarbonate resin (A) and aromatic polyester-polyorganosiloxane block copolymer (B)
), the weight ratio of B and A (A/B)
10/90 to 90/10.