JPH0395256A - Modifier and polyester composition - Google Patents

Abstract

PURPOSE:To improve the moldability, appearance, etc., of a molded product by adding a polyalkylene oxide derivative which has at least one oxystyrene group and wherein the end hydroxyl group is hindered to a polyester resin. CONSTITUTION:A compound of formula I which has at least one oxystyrene group and wherein the end OH group is hindered is used as a modifier for a polyester resin. In the formula, X is the residue formed by removing the hydroxyl groups from a p-hydric hydroxylic compound; Z is the residue formed by removing the hydroxyl group from a monofunctional hydroxylic compound; Y is a styrene group of formula II or III (wherein R and R' are each H, alkyl or halogen); A is 1-4C alkylene; (m) is 0 or a number of 1 or more; (n) is 0 or a number of 1 or more; (p) is 1-8 provided that at least one among (pX(m)) is 1 or more.

Description

[Detailed description of the invention] [Industrial application fields] The present invention relates to modifiers and polyester compositions.

[Prior Art] Polyester resin compositions comprising polyethylene terephthalate, glass fiber, sodium salt of ethylene/methacrylic acid copolymer, and polyethylene glycol dimethyl ether have been known.

[Problems to be Solved by the Invention] However, the above-mentioned polyester resin composition was not satisfactory in both fluidity during melting and appearance during molding.

[Means for Solving the Problems] The present inventors have conducted intensive studies on a modifier that improves fluidity during melting and provides a composition with a good appearance during molding, and a polyester resin composition using the modifier. As a result, we have arrived at the present invention.

That is, the present invention provides a polyester resin modifier comprising a compound (A) containing at least one oxystyrene group and having a terminal hydroxyl group blocked;
A polyester resin composition comprising 60 to 99.8% polyester resin and 0.2 to 40% of the modifier according to any one of claims 1 to 5, based on the weight of the composition. be.

In the present invention, the compound containing at least one oxystyrene group and having a terminal hydroxyl group blocked is a compound having the general formula
(wherein, X is aX of a p-valent hydroxyl group-containing compound,
Z is a residue of a monofunctional hydroxyl group-containing compound, R1 R' is a hydrogen atom, an alkyl group or a halogen atom,
A is alkylene u having 1 to 4 carbon atoms, m is 0 or an integer of 1 or more, n is O or an integer of 1 or more, and p is an integer of 1 to 8. However, at least one of the p m's is 1 or more. ); General formula x-f O-{-Y O・U-1 ``1(-A O
111 ``1 C-Z' Cop
(2) Compound represented by the general formula {-A O rT de Y O voice ting tAO na-i
i-Z ], (3) (where x, Y1Zz At
m1n and p are the same as described in claim 2. l is an integer greater than or equal to 1. ); and the general formula X-mo': C) {-A O )1-=1-1<
Sentence YO zr-15r- [1A O-)11-
b-c − Z′ ko, (in the formula, L
Y% A1ms n and p are the same as described in claim 2. Scarcity is the same as described in claim 4. Z' is the same as described in Item 3. ) are listed.

In the general formulas (1) to (4), the residue of the hydroxyl group-containing compound of X refers to the residue obtained by removing all the droxyl groups from the hydroxyl-containing compound. Hydroxyl group-containing compounds constituting this residue include alcohols, such as aromatic alcohols (benzyl alcohol, phenylethyl alcohol, etc.), aliphatic alcohols (carbon
Alcohols of numbers 1 to 20, such as methyl alcohol, ethyl alcohol, 2-ethylhexyl alcohol, etc.),
Polyhydric alcohols (ethylene glycol, propylene glycol, glycerin, trimethylolethane, trimethylolpropane, etc.), phenols such as phenol, cresol, alkylphenols (carbon atoms 1 to 16)
Phenols having an alkyl group such as nonylphenol, octylphenol, etc.), aliphatic dionoles having 3 to 10 carbon atoms (e.g. propane-1,3-dionole,
butane-1,4-diol, pentane-1,5-diol, hexane-1,6-diol, etc.), carbon number 3-1
5 alicyclic diol (e.g. cyclohexane-1.4
monodimethanol), aromatic diols (such as bis(
4-hydroxyphenyl)methane, 2,2-bis(4-
hydroxyphenyl)propane (hereinafter referred to as bisphenol A)
), bis(4-hydroxyphenyl)sulfone, 2,2bis(4-hydroxy-3.5dibromophenyl)furopane, 2. 2-bis(4-hydroxyphenyl)hexafluoropropane, 4,4'-biphenol, 2,6 dihydroxynaphthalene, etc.) and polyhydric phenols (eg, hydroquinone, etc.).

Among the hydroxyl group-containing compounds of X, preferred are polyhydric alcohols, phenols, and aromatic diols.

The m Y's may be the same or different. Further, m is preferably 1 or an integer of 2 to 30.

Examples of the alkyl groups for R and R' include alkyl groups having t to 4 carbon atoms (such as methyl and ethyl groups), and examples of the halogen atoms include chlorine and bromine atoms. Of R and R', preferred are a hydrogen atom and a methyl group.

Examples of the alkylene group having 1 to 4 carbon atoms in A include methylene, ethylene, propylene, and butylene groups. Preferred are methylene, ethylene, and propylene groups.

A forms an AO (oxyalkylene group) with an oxygen atom, and the n AOs can be the same or different,
The combination format may be random or block type. is preferably an integer from 1 to 30, and n is preferably 0 or l to 30.
O or an integer from 1 to 20 is particularly preferred.

In general formulas (1) and (2), m (YO) and n
(AO) may be connected in any order, or may be connected randomly or in blocks.

p is preferably 1 or 2.

In general formulas (1) and (3), the residue of the monofunctional hydroxyl group-containing compound Z refers to the residue obtained by removing the hydroxyl group from the monofunctional hydroxyl group-containing compound. Examples of the monofunctional hydroxyl group-containing compound constituting this residue include the above-mentioned aromatic alcohols, aliphatic alcohols, and phenols.

Among the monofunctional hydroxyl group-containing compounds (2), aromatic alcohols and aliphatic alcohols are preferred, and particularly preferred are benzyl alcohol and methyl alcohol.

In the general formulas (2) and (4), the residue of the monofunctional carboxyl group-containing compound represented by Z' refers to the residue obtained by removing the carboxyl group from the monofunctional carboxyl group-containing compound. The carboxyl group-containing compounds that make up this residue include aliphatic monocarboxylic acids (formic acid, acetic acid, probionic acid, stearic acid, etc.), aromatic monocarboxylic acids (benzoic acid, naphthoic acid, etc.), and alicyclic monocarboxylic acids. Examples include acids (such as naphthenic acid).

Preferred among the monofunctional lupoxyl group-containing compounds for Z' are aliphatic monocarboxylic acids and aromatic monocarboxylic acids, and particularly preferred are acetic acid, stearic acid, and benzoic acid.

Specific examples of compounds represented by general formulas (1) to (4) include compounds having groups and numbers as shown in Table 1.

Table-1 Ph: Phenyl group Bz: Baseline group E: Ethylene group Me: Methylene group Human: Hysterophenol AR group ■: Hydrogen Me = Methyl! E:
Ethylene group Bz: Penzyl group P
: Phyloxylene group Ph: Phenyl group Compounds of general formulas (1) and (3) are prepared by adding styrene oxide to a hydroxyl group-containing compound, adding alkylene oxide to the compound, and if necessary adding styrene oxide and etherifying the terminal. can get. Or styrene oxide on polyalkylene glycol,
It is obtained by adding anolekylene oxide and etherifying the terminal. In addition, monovalent hydroxyl group-containing compounds include alkylene oxide, styrene oxide,
It can also be obtained by formalizing after addition of alkylene oxide.

The compounds of general formulas (2) and (4) have the terminal c as described above.
It is obtained by esterifying a compound before etherification with benzoic acid.

The modifier of the present invention may be a combination of two or more of the compounds represented by formulas (1) to (4), or may contain other modifiers if necessary. Other modifiers include inorganic solid substances such as talc, metal salts of inorganic and organic acids, metal glycolates, and the like. In this case, the amount of other modifiers is usually 10% by weight or less in the modifier of the present invention.

In the present invention, the polyester resin is obtained by direct esterification or transesterification of a dicarboxylic acid component in which at least 50 mol% is terephthalic acid and a diol component in which at least 50 mol% is ethylene glycol, followed by polycondensation. You get what you get.

O~50 mol% of the dicarboxylic acid component of the polyester resin is other aromatic dicarboxylic acids having e~14 carbon atoms (e.g. phthalic acid, isophthalic acid, 2,6-naphthalenedicarboxylic acid, 4,4-diphenyldicarboxylic acid). , diphenylethane-4,4-dicarboxylic acid, etc.), aliphatic dicarboxylic acids having 4 to 8 carbon atoms (e.g. adibic acid, sebacic acid, etc.) or alicyclic dicarboxylic acids having 8 to 12 carbon atoms (e.g. cyclohexanedicarboxylic acid, etc.) ) etc. may be used.

In addition, 0 to 50 mol% of the diol component is other aliphatic diols having 3 to 10 carbon atoms (for example, propane-1,3-diol, butane-1,4-diol, pentane-1,5-diol, hexane-1, , 6-diol, etc.), carbon number 6
~15 other cycloaliphatic diols (e.g. cyclohexane-
1,4-dimethanol, etc.), aromatic diols having 6 to 12 carbon atoms (eg, bisphenol A, etc.), or polyhydric phenols (eg, hydroquinone, etc.).

Furthermore, oxycarboxylic acids (e.g., ε-oxycaproic acid, hydroxybenzoic acid, etc.) may be copolymerized in an amount of 10 mol % or less of the total dicarboxylic acid component and diol component. Of course, the polyester resin may contain trivalent or tetravalent alcohols (e.g., ethylmethylonolepropane, pentaerythritone, etc.) or tribasic or tetrabasic acids (
For example, it may be branched with trimesic acid, trimellitic acid, etc.).

From an industrial viewpoint, polyester resins are preferably polyethylene terephthalate resins, polybropylene terephthalate resins, and polybutylene terephthalate resins. Its shape may be fibrous or pellet-like.

If necessary, a reinforcing filler can be added to the composition of the present invention to further improve its physical properties. Suitable reinforcing fillers include glass fibers, mineral fibers, talc, mica, kaolin, and the like.

Further, a flame retardant can be added to the composition of the present invention to impart flame retardancy, if necessary. Suitable flame retardants include halogenated diphenyl ether compounds, halogenated polycarbonate compounds, halogenated polyphenylene oxide compounds, halogenated bisphenol resins, halogen-containing S-}riazine compounds, halogenated polystyrene compounds, red Examples include phosphorus-based flame retardants, and if necessary, flame retardant aids such as antimony trioxide and zinc borate may be added to these to develop a synergistic effect.

Furthermore, other additives such as thermal antioxidants, light stabilizers, pigments, Toryo, nucleating agents, plasticizers, lubricants, etc. may be added to the extent that they do not impair discharge.

With respect to the weight of the polyester resin composition, the amount of reinforcing filler added is 0 to 70%, the amount of flame retardant added is 0 to 20%,
The amount of flame retardant aid added is preferably 0 to 15%.

The method for producing the composition of the present invention is not particularly limited, but preferably includes a pelletized polyester resin and a modifier, optionally a reinforcing filler, a flame release agent, a flame retardant aid, and other additives. It can be easily formed by pre-kneading additives and using conventional methods such as extrusion molding and injection molding. For example, extruders: Brabender kneader, Banbury mixer, and other various mixers can be used for kneading, and the kneading temperature ranges from above the melting point of commonly used polyester resins to below 300°C, preferably from 260 to 280°C.
It is ℃.

Alternatively, the composition of the invention can be obtained by adding the modifier of the invention during polyester polymerization.

EXAMPLES The present invention will be explained in more detail with reference to Examples below, but the present invention is not limited thereto.

Parts in the examples are parts by weight.

Example 1 94 parts of phenol and 1.9 parts of potash were placed in a 1L autoclave, replaced with nitrogen, and then replaced with styrene oxide.
120 parts were successively introduced over 3 hours at a temperature of 100° C. while stirring and cooling. After the reaction was completed, 44 parts of ethylene oxide was heated to 100°C with stirring and cooling in the same manner.
It was implemented over time. Then, terminal benzyl etherification was performed by a conventional method to obtain the modifier No. 1 listed in Table 1 of the present invention. 1 to 3
I got 20 copies.

Example 2 62 parts of ethylene glycol and 2.7 parts of potash were placed in a 1L autoclave, the atmosphere was replaced with nitrogen, and then 240 parts of styrene oxide was sequentially introduced at a temperature of 100° C. over 5 hours while stirring and cooling.

Then, terminal benzyl etherification was performed by a conventional method to obtain the modifier of the present invention No. 1 listed in Table-1. Obtained 458 parts of 2 Example 3 Compound 1 before terminal benzyl etherification described in Example 1
20 parts were formalized by a conventional method to form the modifier of the present invention No. 1 listed in Table-1. I got 132 copies of 3.

Example 4 Compound 2 before terminal benzyl etherification described in Example 1
80 parts were esterified with benzoic acid by a conventional method to obtain the modifier No. 1 listed in Table 1 of the present invention. 4, 316 copies were obtained.

Example 5 Compound 3 before terminal benzyl etherification described in Example 2
00 parts were esterified with benzoic acid by a conventional method to obtain No. 00 parts of the modifier of the present invention listed in Table-1. Obtained 445 copies of 5.

Examples 6 to 10 100 parts of polyethylene terephthalate resin, 50 parts of glass fiber, and the modifier No. 1 of the present invention listed in Table 1. 1~
After pre-kneading 3 parts of 5 and extruding and kneading, the mold temperature was 9.
The polyester composition of the present invention was obtained by injection molding at 0°C. Table 2 shows the test results for kneading torque, appearance of a certain shaped product, bending strength and tensile strength.

Example 11 228 parts of bisphenol A and 0.5 part of potash were placed in a 2L autoclave, the atmosphere was replaced with nitrogen, and then 880 parts of ethylene oxide was sequentially introduced at a temperature of 140° C. over 6 hours with stirring. After the reaction was completed, 10 parts of caustic potassium was added, and 240 parts of styrene oxide was successively introduced at a temperature of 100° C. over 3 hours while stirring and cooling. After the reaction was completed, 88 parts of ethylene oxide was successively introduced at a temperature of 140° C. over 2 hours with stirring.

Then, terminal methyl etherification was performed by a conventional method to obtain the modifier of the present invention No. 1 listed in Table-1. Obtained 1,400 copies of 6.

Example 12 228 parts of bisphenol A and loading force IJ 0. After adding 5 parts of ethylene oxide and purging with nitrogen, the temperature was 140°C while stirring 704 parts of ethylene oxide.
It was introduced sequentially over a period of e hours. After the reaction was completed, 10 parts of caustic potassium was added, and 480 parts of styrene oxide was successively introduced at a temperature of 100° C. over 5 hours while stirring and cooling. After the reaction was completed, 88 parts of ethylene oxide was successively introduced at a temperature of 140° C. over 2 hours with stirring.

Then, terminal benzyl etherification was performed by a conventional method to obtain the modifier No. 1 listed in Table 1 of the present invention. I got 1500 copies of 7.

Example 13 32 parts of methanol and 0.0 parts of caustic potassium were placed in a 2L autoclave.
After adding 2 parts and replacing with nitrogen, ethylene oxide 105
6 parts were sequentially introduced over 5 hours at a temperature of 170° C. with stirring. After the reaction was completed, 10 parts of caustic potash was added,
While stirring and cooling 240 parts of styrene oxide,
The introduction was carried out sequentially at 00°C over 3 hours. After the reaction was completed, 88 parts of ethylene oxide was added at a temperature of 14% while stirring.
Sequential introductions were carried out over 2 hours at 0°C. Then, terminal methyl etherification was performed by a conventional method to obtain the modifier of the present invention No. 1 listed in Table-1. Obtained 1,400 copies of 8.

Example 14 32 parts of methanol and 0.0 parts of caustic potassium were placed in a 3L autoclave.
After adding 2 parts and replacing with nitrogen, ethylene oxide 7
A mixture of 0.04 parts of propylene oxide and 464 parts of propylene oxide was successively introduced at a temperature of 170° C. over 5 hours with stirring. After the reaction was completed, 10 parts of caustic potassium was added, and 480 parts of styrene oxide was successively introduced at a temperature of 100° C. over 5 hours while stirring and cooling. After the reaction was completed, 88 parts of ethylene oxide was successively introduced at a temperature of 140° C. over 2 hours with stirring. Then, terminal benzyl etherification was performed by a conventional method to obtain the modifier No. 1 listed in Table 11 of the present invention. 9 to 1
I got 750 copies.

Example 15 94 parts of phenol and 0.0 parts of caustic potassium were added to a 2L autoclave.
After adding 2 parts and replacing with nitrogen, ethylene oxide 4
40 parts were sequentially introduced over 4 hours at a temperature of 170° C. while stirring. After the reaction was completed, 10 parts of caustic potassium was added, and 720 parts of styrene oxide was successively introduced at a temperature of 100° C. over 9 hours while stirring and cooling. After the reaction was completed, 88 parts of ethylene oxide was added at a temperature of 1.
Sequential introductions were carried out over 2 hours at 40°C. Then, terminal methyl etherification was performed by a conventional method to obtain the modifier No. 1 listed in Table 1 of the present invention. Obtained 1300 copies of 10.

Example 16 Compound 2E before terminal methyl etherification according to Example 1
30 parts were esterified with benzoic acid by a conventional method to obtain Modifier No. 1 listed in Table 1 of the modifier of the present invention. 316 copies of 11 were obtained.

Example 17 Compound before terminal methyl etherification described in Example 5 30
0 part was esterified with benzoic acid by a conventional method to obtain No. 0 part listed in Modifier Table-1 of the present invention. 445 copies of 12 were obtained.

Examples 18-24 100 parts of polyethylene terephthalate resin, glass fiber v
150 parts, and the modifier No. 1 of the present invention listed in Table-1. 8
3 parts of 12 were pre-kneaded, extruded and kneaded, and then injection molded at a mold temperature of 90°C to obtain a polyester composition of the present invention. Table 2 shows the test results for kneading torque, appearance of molded products, bending strength, and tensile strength.

Comparative Examples 1 and 2 As comparative examples, Examples 6 to 10 were prepared for the case where no modifier was used (Comparative Example 1) and the case where polyethylene glycol dimethyl ether was used as the modifier (Comparative Example 2),
Table 2 also shows the results for polyester compositions molded under the same conditions as Examples 18-24.

Table 2 [Effects of the Invention] The polyester resin composition of the present invention solves the problem of poor fluidity during molding that conventional compositions have.
The fluidity during melting and the appearance during molding are all satisfactory, and the molded product is easy to mold and has excellent surface appearance. Furthermore, there is no deterioration in the mechanical properties of the molded product.

Due to the above-mentioned effects, the polyester resin composition using the modifier of the present invention can be widely used for molding various molded parts, pipes, containers, etc., and in particular, electrical parts, building material parts, self-contained parts, etc. It can be suitably used for fibers and films. It can also be used for sheets.

Claims (1)

[Scope of Claims] 1. A modifier for polyester resins comprising a compound (A) containing at least one oxystyrene group and having a terminal hydroxyl group blocked. 2. (A) is a general formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (1) (In the formula, X is the residue of a p-valent hydroxyl group-containing compound,
Z is a residue of a monofunctional hydroxyl group-containing compound, Y is a ▲ mathematical formula, chemical formula, table, etc. ▼ or ▲ mathematical formula,
There are chemical formulas, tables, etc. ▼ R and R' are hydrogen atoms, alkyl groups, or halogen atoms, A
is an alkylene group having 1 to 4 carbon atoms, m is an integer of 0 or 1 or more, n is an integer of 0 or 1 or more, and p is an integer of 1 to 8. However, at least one of the p m's is 1 or more. ) The modifier according to claim 1, which is a compound represented by: 3.(A) is a general formula▲There are mathematical formulas, chemical formulas, tables, etc.▼▲There are mathematical formulas, chemical formulas, tables, etc.▼(2) (In the formula, X, Y, A, m, n, and p are The modifier according to claim 1, which is the same as described in claim 2. Z' is a residue of a monofunctional carboxyl group-containing compound. 4. (A) is a general formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (3) (In the formula, X, Y, Z, A, m, n and p are
Same as described. l is an integer greater than or equal to 1. ) The modifier according to claim 1, which is a compound represented by: 5. (A) is a general formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (4) (In the formula, X, Y, A, m, n and p are the same as in claim 2. l is the claim 4. The modifier according to claim 1, wherein Z' is the same as described in claim 3. 6. A polyester resin composition containing 60 to 99.8% polyester resin and 0.2 to 40% of the modifier according to any one of claims 1 to 5, based on the weight of the composition. thing.