JPS585360A - Glass fiber reinforced thermoplastic resin composition - Google Patents

Abstract

PURPOSE:To provide the titled compsn. contg. a vinyl aromatic compd./olefin block copolymer modified with unsatd. carboxylic acid of deriv. thereof and exhibiting improved impact resistance without loss of its inherent properties. CONSTITUTION:The titled composition is prepared from 100pts.wt. thermoplastic resin, 5-250pts.wt. glass fiber, and 1-100pts.wt. modified block copolymer consisting of a vinyl aromatic compd. polymer block A and an olefin compd. polymer block B having a degree of unsaturation of not more than 20%, said block copolymer being modified with a carboxylic acid or derivatives therof. There is not special limitation on the type of thermoplastic resin and glass fiber. The unsat. carboxylic acid is added in an amount of 0.05-20pts.wt., pref. 0.1- 10pts.wt. to 100pts.wt. block copolymer.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention is a method for coating a glass fiber reinforced thermoplastic resin composition. Item 10 relates to a glass fiber reinforced thermoplastic resin composition characterized by containing a block copolymer of a compound and an olefin compound.

Glass fiber-reinforced thermoplastic resin compositions are extremely useful materials because of their excellent properties, such as tensile properties, rigidity, heat resistance, and dimensional stability, but they generally have poor impact resistance. Further, even for materials based on polyamide resins which have relatively excellent impact resistance, further improvement in impact resistance may be required.

Conventionally, rubber-like substances have been effectively used to improve the impact resistance of thermoplastic resins in order to improve the impact resistance, such as ordinary rubbers such as styrene-butadiene rubber, styrene-based or olefin-based thermoplastics, etc. Attempts have been made to add hazy rubber or the like, but the improvement effect has been small and the stiffness has been significantly reduced.

An object of the present invention is to provide a glass fiber-reinforced thermoplastic resin composition with improved impact resistance without impairing its original excellent properties.
We conducted a thorough study on Company H's glass fiber reinforced thermoplastic resin, and as a result, Goodwill O Poly! It was discovered that a glass fiber-reinforced thermoplastic resin composition containing - has extremely excellent impact resistance and also has excellent other properties, and the present invention has been achieved. 100 parts by weight of thermoplastic resin,
(B) Glass fiber! -256 parts by weight, (C) a block copolymer consisting of a vinyl aromatic compound polymer block A and an olefin compound polymer block B, in which the degree of unsaturation of block B does not exceed 20- A glass fiber-reinforced thermoplastic resin comprising 1 to 100 parts by weight of a modified block copolymer (hereinafter simply referred to as "modified block copolymer") in which molecular units containing carboxylic acid groups and derivative groups thereof are bonded. The present invention will be described in detail below.The thermoplastic resin used in the present invention is not particularly limited.

That is, olefin resins such as polyethylene and its copolymer resins, polypropylene and its copolymer resins, 4-methylhene resin, styrene resins such as polystyrene, rubber-modified polystyrene, styrene-butadiene buta ivy copolymer resins, acrylonitrile-butadiene-styrene copolymer resins, acrylonisilyru-styrene copolymer resins, (meth)acrylic acid ester resins, urethane resins, polyamide resins, polyester resins, polyvinyl chloride, and their copolymer resins. One type or a mixture of two or more of polymer resins, polyphenylene oxide and its modified resins, polyacetals, polycarbonates, etc. are used. Among these, olefin resins, styrene resins, polyester resins, polyamide resins, polyphenylene oxides, and their modified resins are more preferable because they have excellent compatibility and are excellent in improving impact resistance. The glass fiber used may be any glass fiber commonly used in glass fiber reinforced plastics. That is, it is manufactured using E glass, C glass, S glass, etc. as raw materials, and its processing form is preferably chopped strand, but depending on the purpose, glass yarn, glass cloth, glass cloth, blown strand, etc. Roving cloth, chiseled strand mat, milled fiber, continuous strand! t,
S-Face! TS) etc. are also used. Furthermore, these surfaces can be treated with a suitable silane coupling agent or the like. The glass fibers are used in a range of S-tS.O parts by weight based on 1 part by weight of the thermoplastic resin. If it is less than 5 parts by weight, the resulting composition 111O stiffness will be low, and if it is more than 5 parts by weight, it will not become brittle, which is not preferable.

Next, the modified block copolymer used in the present invention is synthesized as follows, by way of example. That is, the degree of unsaturation of the conjugated diene moiety of the block copolymer composed of a polymer block mainly composed of a vinyl aromatized metal compound and a heavy metal block mainly composed of a conjugated geno compound does not exceed 50%. By selective hydrogenation to a certain extent and subsequent addition reaction with an unsaturated dicarboxylic acid or a derivative thereof, a modified block copolymer is obtained.

The above block copolymer before hydrogenation contains at least 41, preferably 3, vinyl aromatic compound polymer blocks.
It contains at least one polymer block mainly composed of a conjugated diene compound. Here, the heavy metal block mainly composed of conjugated diene has a weight ratio of vinyl aromatized metal and conjugated diene compound of O/X...~so/
s6. Preferably, it is a polymer block with a composition range of . - those in which the components increase or decrease), partially shaped like a four-piece, or any combination of these O
It may be either. '& O, in the block copolymer before hydrogenation in the present invention, there is a vinyl aromatic compound polymer block, a polymer block mainly composed of a conjugated diene compound, and a vinyl aromatic compound in the O transition @ part etc. A copolymer block of a vinyl aromatic compound and a conjugated diene compound in which the compound exceeds the weight of the compound may be present, but such a polymer block is included in the above-mentioned polymer block mainly composed of a conjugated diene compound. 0 In the above block copolymer, the weight ratio of the content of the vinyl aromatic compound and the content of the conjugated dienated metal is l//
The range of I@=90/1・O is preferable, and the range is from Cape Bond to II/II.
The O range is more preferred.

As the vinyl aromatic compound constituting the block copolymer of the present invention, two or more types are selected from among styrene, α-methylstyrene, vinyltoenene, etc., and styrene is particularly preferred.

Moreover, as a conjugated diene compound, butadiene, isoprene, 1. ) pentadiene and the like, among which butadiene and /l or imprene are preferred for the buttock. The block copolymer has a number average molecular weight of 2, coo-son, oa.
The molecular weight distribution (ratio of weight average molecular weight to number average molecular weight) is
The range of x, oi-no is preferred.

The molecular structure of the block copolymer may be linear, 5-strand, radial, or a combination thereof.

Furthermore, when butadiene is used as the conjugated diene compound in the block copolymer, the amount of 14 bonds in the 01 structure of the butadiene moiety is preferably in the range of 10%,
The range of 35 to Uchi is more preferable.0 When the above block copolymer contains two or more blocks mainly composed of a vinyl aromatic compound or a block mainly composed of a conjugated diene compound, each The components may have the same structure, and the content of the seven components,
They may have different structures such as the distribution in molecular IsK, the molecular weight of the block, and the Miku p structure table.

The block copolymer of the present invention is usually produced by combining a vinyl aromatic compound and a conjugated diene compound in an inert hydrocarbon solvent such as penzel, toluene, hexane, or cyclohexane using an organic lithium compound such as butyllithium as a catalyst. It is obtained by anionic living polymerization method. Furthermore, the block copolymer having lithium active terminals obtained by the above method can be reacted with a polyfunctional coupling agent such as carbon tetrachloride, silicon tetrachloride, etc.
□9, 0-strand iJ that can be made into a branched or radial block copolymer! In this case, any block copolymer obtained by any heavy metal method can be used as long as it falls within the above range. Furthermore, block copolymers can be used not only as a single type but as a mixture of two or more types. It is also possible.

The above block copolymer can be prepared by a known method such as
4! -117・The part where the aromatic double bond OX/- of the vinyl aromatic compound block is not ζ due to hydrogenation according to the method described in the number publication, and the aliphatic double bond of the conjugated diene compound plotter. A partially hydrogenated block copolymer in which 4so* is hydrogenated is synthesized.

In the present invention, the block BO unsaturation degree refers to the block BK
The proportion of longitudinal fiber-carbon double bonds included is 0, which is reflected in the nuclear magnetic resonance absorption spectrum (NMR), infrared'
The partially hydrogenated block copolymer is then treated with an unsaturated carboxylic acid or its derivative. It is modified by the addition reaction of Examples of derivatives of unsaturated carginic acid added to the partially hydrogenated block copolymer include maleic acid,
maleic anhydride, fumaric acid, itaconic acid, acrylic acid,
Kutonic acid, cis-4-7 chlorohexene-1. Dicarboxylic acids and their anhydrides, dicarboxylic acids and their anhydrides,
Goose.

Z,

The above-mentioned modified block copolymer, which is a component of the composition of the present invention, is prepared by adding an unsaturated carboxylic acid or a derivative thereof to the base block copolymer in a solution state or a molten state, using or using a radical initiator. It can be obtained by adding it without removing it. Regarding the manufacturing method of these modified block copolymers, although there are no particular limitations in the present invention, if the obtained modified block copolymer contains undesirable components such as gel, its melt viscosity increases significantly. A manufacturing method involving paper-making that deteriorates processability is undesirable.For example, an unmodified Pututa copolymer is reacted with an unsaturated carboxylic acid or a derivative thereof in the presence of a radical initiator in an extruder. There is a way to make it 1.

The amount of unsaturated carboxylic acid or its derivative added to the block copolymer is 1) per 101 parts by weight of the block copolymer.
o, es −x, · parts by weight are preferable, and 0.1 to 1 ·
Parts by weight are more preferred. When the added amount is less than the weight part of O,OS and it is made into a linear material, there is only a slight improvement compared to the unmodified block copolymer, and even if the added amount exceeds the weight part, the There is almost no increase in the effect of improvements compared to the following. The unsaturated carboxylic acids or derivatives thereof used in the present invention can be used not only alone but also as a mixture of two or more.

The modified block copolymer is used in an amount of 1 to Zoo0 parts by weight per 100 parts by weight of the thermoplastic resin.

If it is less than 1 part by weight, no impact resistance improvement effect can be found;
If it exceeds 0 parts by weight, the stiffness of the resulting composition will decrease.

The glass fiber-reinforced thermoplastic resin composition of the present invention can contain various additives that are added under electrical current, such as antioxidants, ultraviolet LS absorbers, colorants, fillers, organic peroxides, and the like.

The production of the glass fiber reinforced thermoplastic resin composition of the present invention includes:
A method using a kneading machine such as a screw extruder, a pan-barrier kneader, a Nigu, a mixing roll, a method of laminating with a press molding machine, a solution impregnation method, a powder impregnation method, etc. can be used.Examples are shown below. . Although this example is representative of the present invention, it is not intended to limit the scope of the present invention.

The physical properties in the Examples were measured using the methods shown below.

Physical properties Measurement method Tensile strength JI! i-to? 111 (1
No. test piece) Bending strength Mu8TM-D
71Gllhke elastic modulus M8? M-Dys.

In addition, the Kuenshi block copolymer used in this example was prepared by the method described below.

(1) Hydrogenated block copolymer 01111 Using n-butyl lithium as a polymerization catalyst, n-hemanane was used as an anion, and tetrahydrogen was used as a vinyl content regulator in a cyclohexane solvent. Through Plutz copolymerization, block copolymers as shown in Table 1 were synthesized.

Table 1 Styrene-butadiene block copolymer Next, the block copolymers shown in Table 1 were mixed in a mixed solvent of 凰-hexano and Schiff-tetrahexane.
Using rietheralunium as a catalyst, the hydrogen pressure was 7 Kg/
d, Hydrogenation was carried out at a temperature of 0 °C for S hours, and about 1 ie of the double bond in the butadiene plotter part was hydrogenated, and almost all the benzene ring lines in the styrene fermentation part remained unhydrogenated. A hydrogenated block copolymer was synthesized. The O metal remaining on the catalyst was removed by washing with an aqueous hydrochloric acid solution and methanol. Preparation of modified block copolymer (2) Parts by weight of anhydrous maleic acid and L1 parts by weight of Perhequina 1sB (manufactured by NOF Corporation) were uniformly mixed, and then placed in a screw extruder (single screw, screw diameter added, L/D-24, full size) under a nitrogen atmosphere. flight type screw)
9. The maleation reaction is carried out at a cylinder temperature of sO ℃. From the obtained modified block copolymer, unreacted anhydrous! Leic acid is removed under reduced pressure and used as a stabilizer! , 6-sheeter 4-methylphenol, 10 parts by weight of the polymer,! When the O-O-modified Bootsk copolymer added in parts by weight was analyzed, the expected results were obtained.

The amount of maleic anhydride O added to the modified Prusk copolymer was measured by titration with sodium methylate.

Hydrogenated Plutz copolymer 1, which was threatened in (1) above,
...impregnated with 2.5 parts by weight of acrylic acid and uniformly mixed with 0.1 parts by weight of Perhequina 25 B, and then supplied to a screenie Taki extruder under a nitrogen atmosphere.
The modification reaction was carried out at a cylinder temperature of 1°C. From the obtained modified straw ivy copolymer, unreacted acrylic acid was removed under reduced pressure by heating, and 1 part by weight of -4-methylphenol was added to 2.6-sheeter yearly petite as a stabilizer. Added 9 parts by weight of o and s. When this modified block copolymer was analyzed, a surface SO bond was obtained.

Table 3 The amount of acrylic acid added was determined by titration with sodium methylate.

Examples 1 to I Various types of funbound made of thermoplastic resin, modified Plutz copolymer, and glass fiber were mixed using a pressure kneader at a mixing temperature of about 21°C and a kneading time of 15 minutes. Further, these compounds were made into a molded plate having a thickness of 3u using a hot press at 200°C.

1m! 4 shows the measurement results of these compositions and physical properties ◇ Comparative Example 1-4 Various types of compounds made of thermoplastic resin and glass fiber were kneaded at a kneading temperature of about 21 e°C and a kneading time of 1 s. Below,
fCo was produced using a pressure kneader.Furthermore, these compounds were made into a molded plate with a thickness of 3 ms using a hot press at 200°C.

Comparative Example s-i Various compounds consisting of a thermoplastic resin and a modified block copolymer were mixed at a kneading temperature of about 210°C and a mixing time of ls. It was manufactured using a pressure kneader as described below. Furthermore, these molded plates were molded into a 3 m thick molded plate using a hot press at OO°C.

Comparative Example 7 Table 4 shows the results obtained in the same manner as in Example S except that the amount of glass fiber was changed to 800 parts by weight. .

Comparative Example a Comparative Example A was obtained in the same manner as in Example except that the amount of glass fiber was changed to 200 parts by weight. The results are shown in Table 4.

Comparative Example 1 A product obtained in the same manner as in Example I except that the hydrogenated block copolymer before modification of the axillary modified block copolymer M(I) was used instead of the modified block copolymer M(I). The results are shown as *aK.

Comparative Example 10 Obtained in the same manner as in Example 1 except that a hydrogenated block copolymer before modification of the modified block copolymer M(I) was used instead of the modified block copolymer M(I). The results are shown in Table 4.

Below is a blank space Example 9 In Example I, modified block copolymer M (I)0
Instead, the results are shown in Table 5. The results are shown in Table 5. The results are shown in Table 5. The results are shown in Table 5.

Example 10 The same procedure as in Example I was carried out except that instead of modified block copolymer M(I), modified block copolymer M(I) treated with hot water (immersed at 80° C. for 3 hours) was used. The results obtained are shown in lls.

Example 11-1! Various compounds consisting of thermoplastic resin, modified Plutz copolymer M (I), and glass fiber were manufactured using a 460φ extruder at 290°C for polyamide and 230°C for modified polyphenylene oxide. These compounds were then molded into 3-inch thick flat plates using an 1 ounce injection molding machine. Table 6 shows the compositions and measurement results of physical properties.

Comparative Examples 11-12 Various compounds made of strong plastic resin and glass fiber were manufactured under the same conditions as in Example 11-1, and flat plates with a thickness of 3 mm were injection molded. Table 6 shows the measurement results of these blending compositions and physical properties. Comparison Example 13, Comparative Example 13 A compound consisting of polyester resin, modified block copolymer C (It), and glass fiber was heated at 250°C. in,
The compound was manufactured using a φ extruder, and then the compound was molded into a 3-inch thick flat plate using a one-ounce injection molding machine. Table 7 shows the results of measuring the physical properties of this compound. For comparison, Table 7 also shows the results when a compound consisting only of polyester resin and glass fiber was used.

As shown in Tables 4 to 7 below, the glass fiber-reinforced thermoplastic resin composition of the present invention has extremely high impact resistance and hardly reduces other mechanical strengths. Rather, it is an excellent composition that improves performance.

Patent applicant: Asahi Kasei Industries, Ltd.

Claims (1)

[Claims] (A) 100 parts by weight of thermoplastic resin, (B) Glass fiber s
-zso parts by weight, (C) A block copolymer consisting of a vinyl aromatic compound polymer block B and an olefin compound polymer block B, the block copolymer having a block BO unsaturation degree of 2051 or less. , a glass fiber-reinforced thermoplastic resin composition comprising 1 to 1.0 parts by weight of a modified block copolymer to which molecular units containing carmenic acid groups or derivative groups thereof are bonded.