JPH04153253A - Polyester resin composition and polycarbonate resin composition - Google Patents

Abstract

PURPOSE:To obtain the title composition improved in hydrolysis resistance by mixing a polyester resin or a polycarbonate resin with a specified epoxy resin. CONSTITUTION:A thermoplastic polyester resin or a polycarbonate resin is mixed with an epoxy resin comprising an open-ring lactone of the formula (wherein X is an epoxy group of formula II; R<a> and R<b> may be the same or different and are each H, methyl, isopropyl, n-butyl, sec-butyl or t-butyl, c is 1-7, and n is 1-20) to obtain a polyester or polycarbonate resin composition improved in heat and hydrolysis resistances. The amount of the epoxy resin added is usually 0.1-10wt.%, particularly desirably 0.5-4wt.% based on the polyester or polycarbonate.

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a thermoplastic polyester resin composition and a polycarbonate resin composition with improved heat resistance and hydrolysis resistance.

(Prior Art) Thermoplastic polyester resins and polycarbonate resins have well-balanced physical properties and excellent moldability, and are widely used in mechanical parts, electronic parts, automobile parts, and other fields.

However, polyester resin has a major drawback in that it is easily hydrolyzed due to ester bonds.

Furthermore, polycarbonate resin contains chlorine as an impurity, which causes molded products to lack stability.

In order to overcome these drawbacks, a method of adding polycarbodiimide, which is a hydrolysis-resistant agent for polyester, has been known for a long time, but although this method improves the durability against hydrolysis, it However, it is expensive and has drawbacks such as discoloration of the polymer when heated for a long time.

In addition, a method of adding an epoxy compound is known, but the epoxy compound has the effect of suppressing the acceleration of hydrolysis by reacting with the carboxyl group generated by hydrolysis or the carboxyl group present at the end of the polyester resin. are doing.

Furthermore, the reaction between chlorine and epoxy groups in the polycarbonate inactivates the chlorine and stabilizes the carbonate bond.

As for the epoxy compounds used, compounds with smaller epoxy equivalents have a greater effect.

Therefore, low molecular weight epoxy resins are used.

However, since low molecular weight epoxy resins are usually liquid, if too much is used, the properties of the polyester resin will deteriorate.

As solid epoxy resins, there are epi-bis type epoxy resins and novolac type epoxy resins, but these have the drawbacks of being less effective and coloring because of their large epoxy equivalents.

(Problems to be Solved by the Invention) In view of this situation, the inventors of the present invention have made extensive studies and have found that by adding the compound of formula (1) to polyester resins and polycarbonate resins, the hydrolysis resistance of the polyester resins and polycarbonate resins can be improved. They discovered that this could be significantly improved and completed the present invention.

(Structure of the Invention) That is, the present invention provides a thermoplastic polyester resin containing the following general formula (1)% formula% [In the general formula (+), X is the following formula Ra Rb; hydrogen, methyl, isopropyl, n-butyl, The 5ec-butyl\tert-butyl group and RaRb can be simultaneously replaced with each group.

c: an integer of c-1 to 7 n; a thermoplastic polyester resin blended with an epoxy compound represented by an integer of n-1 to 20" and "a polycarbonate resin with the following general formula (+)ORO II I 11 x-c→-0→(iii)-C-+-OCH2-XCn Rb (1) [In general formula (1), X is the following formula b.

R, R, hydrogen, methyl, isopropyl, n-butyl, 5
A polycarbonate resin composition containing an epoxy compound having an ec-butyl or tert-butyl group and represented by RaRb.

Next, the present invention will be explained in detail.

In the epoxy resin represented by the (+) formula blended into the thermoplastic polyester resin or polycarbonate resin composition of the present invention, Ra and Rb are hydrogen, methyl, isopropyl, n-butyl, sec-butyl, and tert-butyl, respectively. It can be changed to the base of

C is an integer of 1-7, and n is an integer of 1-20.

This indicates that the structure represented by Ra 0 -O-+C+-C→-CnRb is generated by ring-opening of a lactone.

For example, when using ε-caprolactone, the formula (+) is X-C+-O+CH-r+TC÷--OCH2-X[A
] [However, or in the following formula, n is the number of moles of inserted ε-caprolactone.

Also, this is rough with c-5 to for the number of carbon atoms in the ring of respond.

In the case of β-methyl-δ-valerolactone, +1 C-+-O C+-0CH2 [B] [However, X is the following formula % formula %] [] [However, X is the following formula % formula % X -C- +O-Z +OCH2
It is possible to obtain a structure in which the structures of the lactone moieties of A], [B], [C], and [D are randomly combined.

Since these have a molecular weight distribution, n here is the average number of added moles of lactone inserted.

The thermoplastic polyester resin which is the main organism of the thermoplastic polyester resin composition of the present invention is terephthalic acid or its esters, ethylene glycol, propylene glycol, butanediol, bentanediol, neopentyl glycol, hexanediol, octanediol,
Decanediol, cyclohexane dimetatool, )\hydroquinone, bisphenol-A, 2,2-bis(4-
Terephthalic acid-based polyester resins obtained from glycols such as hydroxyethoxyphenyl)propane, 1.4 dimethyloltetrabromobenzene or the ethylene oxide adduct of tetrabromobisphenol-A1, isophthalic acid, orthophthalic acid, naphthalene dicarboxylic acid , 44'-diphenyldicarboxylic acid, diphenyletherdicarboxylic acid, α,β-bis(4-carboxyphenoxy)ethane, adipic acid, sebacic acid, azelaic acid, decanedicarboxylic acid, cyclohexanedicarboxylic acid, or dimer acid. Polyester resins obtained by using dicarboxylic acids or glycols in place of terephthalic acid, such as hydroxybutyric acid, hydroxycaproic acid, hydroxybenzoic acid, hydroxyphenylacetic acid, or hydroxycarboxylic acids such as naphthylglycolic acid, propiolactone, Polymers obtained by polymerizing lactone compounds such as butyrolactone, valerolactone or caprolactone, 2.2'-
Bis(4-hydroxyphenyl)propane, 2,2-bis(4-hydroxy3,5-dibromophenyl)propane, 2,2-bis(4hydroxy3,5-dichlorophenyl)propane, 4,4-dihydroxydiphenyl sulfone, 4,4'-dihydroxydiphenyl ether,
4.4--dihydroxydiphenyl sulfide, 4.4
゛-dihydroxydiphenyl-ketone, 4.4'-dihydroxydiphenylmethane, 2.2-bis(4-hydroxy3,5-methylphenyl)-propane, 1.1-bis(4-hydroxyphenyl)-ethane, 1, 1-bis(4-hydroxyphenyl)-cyclohexane, 44-
These include aromatic polyesters obtained from bisphenols such as monodihydroxydiphenyl-methyl-isobutyl-methane and aromatic polybasic acids.

Among these thermoplastic polyester resins, particularly preferred effects are exhibited when polybutylene terephthalate and polyethylene terephthalate are used.

The polycarbonate resin used in the present invention is a polymer or copolymer obtained by a phosgene method in which various dihydroxydiaryl compounds are reacted with phosgene, or a transesterification method in which a dihydroxydiaryl compound is reacted with a carbonate ester such as diphenyl carbonate. It is a polymer, and a typical example is 2,2-bis(
4-Hydroxyphenyl)propane (bisphenol A
) Polycarbonate resins manufactured from

In addition to bisphenol A, the dihydroxydiaryl compounds include bis(4-hydroxyphenyl)methane, 1,1-bis(4-hydroxyphenyl)ethane, 2
．． 2-bis(4-hydroxyphenyl)butane, 2,2
-bis(4-hydroxyphenyl)octane, bis(4-hydroxyphenyl)octane,
-hydroxyphenyl)phenylmethane, 2,2-bis(4hydroquine-3-methylphenyl)propane, 1゜1-bis(4-hydroxy-3-tert-butylphenyl)
Propane, 2,2-bis(4-hydroxy-3-bromophenyl)propane, 2,2-bis(4-hydroxy-
3,5 dibromophenyl)propane, 22-bis(4-
Bis(hydroxyaryl)alkanes such as hydroxy-3,5 dichlorophenyl)propane; 1. l-bis(4hydroxyphenyl)cyclopentane, 1,1-
4. Bis(hydroxyaryl)cycloalkanes such as bis(4-hydroxyphenyl)cyclohexane; 4.
4'-dihydroxy diphenyl ether, 4,4-dihydroxy-3,3-1 dimethyl diphenyl ether,
dihydroquine diaryl ethers such as 4.4'
-Dihydroxydiaryl sulfides such as dihydroxydiphenyl sulfide, 4,4'-dihydroxy-3,3'-dimethyldiphenyl sulfide, 44-1 dihydroxydiphenyl sulfokind, 4,4'-dihydroxy-3,3'-dimethyldiphenyl Dihydroxy diallyl sulfoxides such as sulfoxides, 4.4
Examples include dihydroxydiarylsulfones such as --dihydroxydiphenylsulfone and 4,4'-dihydroxy-3,3''-dimethyldiphenylsulfone.

These can be used alone or in a mixture of two or more,
In addition to these, piperazine, dibiperidyl, hydroquinone, resorcinol, 4,4-dihydroxydiphenyl, etc. may be used in combination.

In the present invention, the epoxy resin blended with the polyester resin and polycarbonate resin is usually 01 to 10% of the polyester resin or polycarbonate resin.
It is preferably 0.5 to 4% by weight.

If the amount is less than 0.1% by weight, the effects on heat resistance and water resistance will be reduced, and if it exceeds 10% by weight, the properties of the polyester resin composition and polycarbonate resin composition will deteriorate.

The Epoquin compound and the polyester resin and polycarbonate resin are usually mixed by melt mixing.

4 of the thermoplastic polyester resin in the composition of the invention.
A small proportion of 0% by weight or less is used, for example, in polyolefins, ionomers, polystyrene, AS resins, ABS resins, MB
S resin, ASA resin, acrylic resin, vinyl acetate resin,
Polymers such as vinyl chloride resins, ethylene-vinyl acetate copolymers, polyacetals, polyurethanes, polyamides, polysulfones, polyethersulfones or polyroofunicine oxides, or acrylic rubber graftomers, styrene-butadiene rubbers, ethylene-propylene rubbers, polyester-ethers. It may also be in the form of a mixture substituted with various organic polymers such as elastomers or elastomers such as polyamide elastomers.

Furthermore, the composition of the present invention includes glass fiber, titanium sulfate fiber, metal fiber, ceramic fiber, aluminum carbonate, calcium silicate, magnesium silicate, calcium sulfate, barium sulfate, iron oxide, black salt, carbon black, In addition to reinforcing fillers such as mica, asbestos, ceramics, metal flakes, glass beads or glass powder, dyes, plasticizers, mold release agents, lubricants, heat stabilizers, antioxidants, ultraviolet absorbers, blowing agents, flame retardants, A coupling agent or the like may be used in combination.

(Effects of the Invention) The resin composition of the present invention has excellent hydrolysis resistance, gas and heat resistance stability, and therefore has great industrial utility, including electrical, electronic parts, mechanical parts, automobile parts, and building material parts. In addition to traditional uses such as , tool storage boxes, power tool lids,
It can also be used in large molded products such as sporting goods, bearings, and automobile bumpers, in equipment used in cold regions, and in the fields of textiles, films, and adhesives.

Synthesis example-1 2J7 equipped with a nitrogen introduction tube, thermometer, cooler, and stirring device
1211.7 gr, ε-caprolactone 6269 g in the flask
8.51 g of r% diethylene glycol, 1% hebutane solution of tetrabutyl titanate as catalyst, 9. '2
0 gr was added and heated at 220° C. for 27 hours while passing nitrogen through.

The remaining caprolactone was 0.16% by weight.

Synthesis examples-2 to 3 The reaction was carried out in the same manner as in Synthesis Example 1 using the ingredients shown in Table 1.

Table shows the charging ratio of each raw material and the physical properties of the obtained compound.
Shown in 1. (Leaving space below) Synthesis Example-4 Put 167.2g of the compound obtained in Synthesis Example-1 and 150.0g of ethyl acetate into a 2000cc flask equipped with a thermometer, cooler, stirrer, and cooling jacket. It was kept at 50°C.

A peracetic acid solution (concentration 30%) and 1.4 gr of sodium 2-ethylhexyl tripolyphosphate were added dropwise to this over 2 hours.

Thereafter, the mixture was kept at 50° C. for another 2 hours, and the peracetic acid concentration of the reaction crude solution was reduced to 0.1% or less.

Add 320g of ion-exchanged water to the resulting reaction crude liquid.
The mixture was stirred at 50° C. for 0 minutes.

This was allowed to stand for about 40 minutes to separate into an upper layer and a lower layer. The lower layer was gradually removed over a period of about 20 minutes.

150 ml of ethyl acetate was added to the remaining upper layer, and the same operation was repeated two more times under the same conditions.

The obtained upper layer liquid was subjected to low boiling treatment using a glass Smith type thin film evaporator.

The operating conditions were a heating temperature of 150° C. and a pressure of 10 mmHg.

The yield was 95% based on the amount of the dehydrated liquid obtained.

Synthesis examples 5-6 The reaction was carried out under the conditions shown in Table 2 in the same manner as in Synthesis Example 4.

Table shows the charging ratio of each raw material and the physical properties of the obtained compound.
Shown in 2.

Example 1 PET [CN9030 manufactured by Ondai Co., Ltd.]: 2 parts by weight of the compound of Synthesis Example 6 was blended with 100 parts by weight, and the mixture was kneaded into pellets using a twin-screw vent extruder at 210''C.

Samples for physical property tests were made from the pellets at a temperature of 290°C and a mold temperature of 80°C.

Example-2 PBT [Polyplastic Co., Ltd. 2012] 100
2 parts by weight of the compound of Synthesis Example-5 was blended with the weight part, and the mixture was kneaded into pellets at 240°C using a twin-screw vent extruder.

Samples for physical property tests were prepared from the pellets at a temperature of 250°C and a mold temperature of 60°C.

The mechanical properties of the cured products of the compositions obtained in each example are shown below.
Shown in 3. (The following is a blank space) The heat and humidity resistance test was conducted at 100°C x 95RH, and a value of 24 hours was obtained.

Example 3 3 parts by weight of the compound of Synthesis Example 4 was blended with 100 parts by weight of bisphenol A type polycarbonate having a molecular weight of 23,000, and the mixture was kneaded at 280°C in a twin-screw vent extruder and pelletized.

After drying the pellets with hot air, samples for physical property tests were prepared using a 3.602 injection molding machine at a molding temperature of 300°C and a mold temperature of 80°C.

Example 4 The same procedure as Example 3 was carried out except that 2 parts of the compound of Synthesis Example 2 was added using bisphenol A type polycarbonate having a molecular weight of 1119,000.

The heat and humidity resistance of the molded product was as shown in Table 4 below.

The heat and humidity resistance test was conducted at 100°C and 95RH, and a value of 24 hours was obtained.

Claims (2)

[Claims] (1) Thermoplastic polyester resin with the following general formula (I)
▲There are mathematical formulas, chemical formulas, tables, etc.▼……(I) [In the general formula (I), , n-butyl, sec-butyl, and tert-butyl groups, and RaRb can be simultaneously replaced with each group. c: an integer of c=1 to 7; n: an integer of n=1 to 20] A thermoplastic polyester resin blended with an epoxy compound represented by the following. (2) Polycarbonate resin has the following general formula (I)▲There are mathematical formulas, chemical formulas, tables, etc.▼……(I) [In the general formula (I), X is the following formula▲There are mathematical formulas, chemical formulas, tables, etc.▼ R ^a, R^b: A polycarbonate resin composition containing an epoxy compound represented by hydrogen, methyl, isopropyl, n-butyl, sec-butyl, or tert-butyl group, where RaRb is.