JPS5898354A - Thermoplastic resin composition - Google Patents

Abstract

PURPOSE:To provide a thermoplastic resin compsn. having excellent processability and resistance to impact and weather as well as excellent weld strength, consisting of a compsn. contg. a polycarbonate resin and a specified graft polymer and a specified plasticizer. CONSTITUTION:A compsn. consists of 100pts.wt. compsn. (A) consisting of 20- 80wt% polycarbonate resin (A-1) and 80-20wt% mixture (A-2) composed of 100-10wt% graft polymer composed of an ethylene/propylene rubbery compolymer and at least two compds. selected from each of at least two groups selected from among arom. vinyl compds., vinyl cyanide compds. and other polymerizable monomers, and 0-90wt% copolymer composed of at least two compds. selected from each of at least two groups selected from among arom. vinyl compds., vinyl cyanide compds. and other polymerizable monomers, and 0.5-20pts.wt. plasticizer (B) in which a film prepd. from 0.25g of said plasticizer and 0.75g of an acrylonitrile/styrene copolymer (30:70wt. ratio) has a light transmittance of 70% or above.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a novel thermoplastic resin composition that has excellent impact resistance, weather resistance, processability, and weld strength.

Polycarbonate resin (hereinafter referred to as PC) is widely known as an engineering plastic with excellent impact resistance and heat resistance. In addition, we have reduced the price of PC and improved the thickness dependence of moldability and impact strength.
Mixture of C and ABS resin (acrylonitrile-diene rubber-styrene polymer) (% Kosho 38-1522!5
), PC and AES* with improved weather resistance and stain resistance
fat (acrylonitrile - ethylene/propylene rubber)
styrene polymer) (JP-A-48-48547
) etc. are also widely known.

However, PC-AES resin compositions tend to cause flow marks and delamination on the surface of the molded product, and in injection molding, which is the most common molding method, the number of gates and the number of gates vary depending on the shape and size of the molded product. The flow state of resin must flow in different directions in order to change the flow state of the resin.61
! A so-called l-weld part I occurs where the fat intersects, but in conventional compositions, the strength of the weld part, the l-fel strength I, is insufficient from the viewpoint of practical moldability, and it is not suitable for practical use. At present, there are few materials that are excellent for this purpose.

The present inventors have discovered that such polycarbonate resin and AE
We conducted extensive research on improving the weld strength of resin compositions consisting of S resin and found that polycarbonate resin and AES
It was discovered that by adding a certain percentage of plasticizer to a composition consisting of a resin, a composition having excellent impact resistance, weather resistance, heat resistance and processability as well as weld strength can be obtained, and the present invention has been made based on this discovery. The following one arrived: 〇 That is, misfire 8A is polycarbonate resin (A-1) 20-80
Resin composition (A) consisting of 80 to 201 tS of AES resin (A-2) 1001 parts by weight, 0.2 parts of plasticizer
57 all acrylonitrile loose delene (mlit ratio 30 near 0) copolymer 0.75 F with 10 tl of acetone
The light transmittance of the 20μ film made by dissolving Vc is 70
The present invention provides a thermoplastic resin composition characterized by comprising 0.5 to 20 parts by weight of a plasticizer (B) of at least 100% by weight.

The thermoplastic resin composition of the present invention will be explained in detail below.

Examples of the polycarbonate resin (A-1) include aromatic polycarbonate, aliphatic polycarbonate, aliphatic-aromatic polycarbonate, etc. Generally, lj, 2,2-bis(4-oxyphenyl)alkane, bis( 4-oxyphenyl)ether, bis(4-
Oxyphenyl) sulfone, sulfide, or t is a polymer or copolymer made of bisphenols such as sulfoxide type, and is a copolymer using a bisphenol substituted with a halogen depending on the purpose.

The ethylene-propylene rubbery copolymer constituting the graft polymer (A-2-1)e is
These include a binary copolymer made of propylene (EPR), a terpolymer made of ethylene, propylene, and a non-conjugated diene (EPDM), and more than one copolymer is used.

Examples of the non-conjugated diene in the ternary combination (EP DM) include dicyclopentadiene, dennorbornene, 1.4-hexadiene, 1.4-cycloheptadiene, 1.5-cyclooctadiene, etc. Binary copolymers (EPR) and tertiary copolymers (EPDM)
) is the molar ratio of ethylene and propylene 5:1?
It is preferable that the ratio is 1:3.

In the ternary copolymer (EPDM), it is preferable that the proportion of non-conjugated diene is in the range H of 2 to 50 in terms of iodine value.

Graft polymer (A-2-1) and copolymer (A-2
Examples of the aromatic vinyl compound constituting -2) include styrene, α-methylstyrene, α-chlorostyrene, and vinyltoluene, with styrene being particularly preferably used.

Examples of vinyl cyanide compounds include acrylonitrile and methacrylonitrile, with acrylonitrile being particularly preferably used.

Further, other polymerizable monomer compounds include acrylic ester compounds and methacrylic ester compounds such as methyl, ethyl, furovir, methyl, benzyl, and hexyl, with methyl methacrylate being particularly preferred. 0 One or more compounds each selected from at least two of the above-mentioned aromatic vinyl compounds, vinyl cyanide compounds, and other polymerizable monomer compounds are used.0 The weight of these compounds and the rubbery copolymer An appropriate range of ratios can be selected depending on the purpose. Normal compound 95
-40% by weight of the rubbery copolymer 5-60% by weight, preferably 95-75% by weight of the compound and 1% by weight of the rubbery copolymer.

As a method of polymerizing a compound to produce the graft polymer (A-2-1) in the presence of a rubbery copolymer, all known methods can be used, such as suspension polymerization, bulk polymerization, 0 Mixture (A-2) is a graft polymer (A-2-1) 10
0-10% by weight ↓ and copolymer (A-2-2) O-90
The 0-co-1 polymer (A-2-2) consisting of t% by weight is 90][i
i more than 1%, that is, the graft polymer (A-2-
If 1) is less than 10% by weight, sufficient impact resistance cannot be obtained. 0 Resin composition (N is the above-mentioned polycarbonate (A-1)
) 20-80% by weight and mixture - (A-2) 80-20
Weight% is better. If the amount of polycarbonate (A-1) is less than 20% by weight, the heat resistance will be significantly lowered, which is undesirable. If it exceeds 80% by weight, the workability will be decreased and the weld strength will not be improved. Preferably polycarbonate (A-1
) 30-70% by weight.

The plasticizer used in the present invention is obtained by dissolving the plasticizer 0.25F together with the acrylonitrile-styrene copolymer 0.751 in A7Tone 10- and drying it naturally to form a film with a thickness of 20μ and the light transmittance at t. Filter with a plasticizer of 70% or more.

A plasticizer with a light transmittance of less than 70% cannot achieve the object of the present invention. Furthermore, the plasticizer bleeds into the narrow surface of the final composition, which is undesirable.

In addition, the above-mentioned acrylonitrile-styrene copolymer means a copolymer consisting of 3.0 parts by weight of acrylonitrile and 70 parts by weight of styrene.

To further explain the types of plasticizers (B), dicarboxylic acids such as phthalic acid, adipic acid, sebacic acid, azelaic acid, maleic acid, fumaric acid, trimellitic acid, citric acid, itaconic acid, and ricinoleic acid. Ester plasticizers with monohydric alcohols or dihydric alcohols such as ethylene glycol and fluoropylene gellicol, epoxy plasticizers with epoxy groups in the molecule, and phosphate esters such as diphenyloctyl phosphate and trioctyl phosphate. In addition, from the viewpoint of volatility, the ester plasticizer is preferably a polymer type in which several or more ester structural units are connected, rather than a seven-mer type in which one ester structural unit is used.

One or more of these plasticizers can be used.

The plasticizer (B) is 0.5 parts per 100 parts by weight of the composition (A) consisting of polycarbonate (A-1), graft polymer (A-2-1) and co-1 polymer (A-2-2). ~20]
i[ii part is used. If it is less than 0.5 Jll, the queld strength will not be improved, and the flexibility and formability will not be improved either. On the other hand, if the amount exceeds 20 parts by weight, the heat resistance will drop significantly, which is not preferable.

The addition of the plasticizer can be carried out using a known device, and known additives such as stabilizers, antistatic agents, lubricants, dyes and pigments may be appropriately added during the addition and mixing.

Examples will be described below, but the present invention is not limited to these in any way.

Examples and Comparative Examples The polycarbonate resin, graft polymer, and copolymer were kneaded with a chewing agent in a Banbury mixer in the proportions shown in Tables 1 and 2 to form compositions (compositions A1 to 22). t-
Nine points.

Various test specimens were prepared from the obtained composition. The test results are shown in Tables 3 and 4.

The compositions and manufacturing methods of the nine polycarbonate a resins, graft polymers, and copolymers used are as follows.

(A-1) Polycarbonate resin manufactured by Teijin Kasei Co., Ltd. L 1250W# (A
-2-1) Graft polymer a EPDM (iodination 8.5, Mooney viscosity 61°, propylene content 43% by weight, ethylidene norbornene as non-conjugated diene component) 300 parts by weight tn-hexane After dissolving in 2000 parts by weight and 1500 parts by weight of ethylene dichloride, adding 1 part by weight of Styrene Fluo 01L, 300 parts by weight of acrylonitrile and 10 parts by weight of benzoyl peroxide, the mixture was heated at 67°C for 10 hours in a nitrogen X atmosphere at 600 r, p.
, m, under stirring. The polymerization solution was brought into contact with a large excess of methanol, and the precipitate was separated and dried to obtain a polymer (rubber content: 28.2%).

(A-2-2) Copolymer ■ Styrene 70! t% and acrylonitrile 30 wt S
0.1 part by weight of t-dodecylmercaptan was added to 100 parts by weight of a mixed solution, and prepolymerized in bulk at 90°C for 3 hours, and then 2101 Lt parts of water and 1.
0 parts by weight and 0.3 parts by weight of benzoyl peroxide were added, the temperature was raised from 30°C to 90°C in an aqueous dispersion system, and the mixture was stirred for 10 hours. After dehydration, a copolymer (intrinsic viscosity O, SO) was obtained.

Copolymer ■ Commercially available stene-acrylonitrile copolymer (intrinsic viscosity [
01 $ 3), Sebian NJDI manufactured by Daicel Chemical Co., Ltd. Measurement method of ray transmittance] 30 parts of acrylonitrile, 70 parts of styrene, 0.4 parts of dodecyl mercaptan, and 0.0 parts of shivaloyl oxide.
After adding 5 parts and carrying out zero substitution to prepare the polymerization system, 3.
The above prepolymer (total molar polymerization rate 26.7%) was mixed in 200 parts of Kyu water with 0.14 parts of polyvinyl alcohol% and 0.06 parts of methylcellulose as suspension stabilizers.101. 1 part was suspended, 0.5 part of lauroyl peroxide was added as a radical polymerization initiator, 4 parts of supplementary amount of acrylonitrile eluted into the aqueous phase, and 0.19 f of acidic sodium sulfate were added as an aqueous phase polymerization inhibitor at 70°C. Soak it for 3 hours. In order to remove the secondary granular polymer obtained by suspension polymerization and unreacted upper particles, the granular polymer was separated by stripping with 150°C steam for 3 hours, washed and dried to obtain a copolymer. .

0.751% of nine acrylonitrilethrene co-1 obtained by the above method, 0.255% of elm plasticizer and gold (total 15
F) was dissolved in 10 ml of amethyst, air-dried to form a film with a thickness of 20 μm, and the light transmittance was determined using a haze meter 5EP-H-2 manufactured by Nippon Seimitsu Kogaku.

x2. Otm) L') Molten resin (260'C
) i Injection, create a test piece with a thickness of 3cm and a vertical and horizontal valley of 150sa*.

Test piece complete jig (height 8o, inner diameter 120m, outer diameter 126mm)
■).

A 1# steel ball is dropped onto the center of the test piece in a cold room adjusted to -30℃, and the maximum energy value (
#・Part) wo seek.

patent applicant Sumitomo Naugatuck Co., Ltd.

Claims (1)

[Claims] Polycarbonate resin (A-1) in an amount of 20 to sas, an ethylene-propylene rubbery copolymer, an aromatic vinyl compound, a vinyl cyanide compound, and other polymerizable monomer compounds A graft polymer (A-2-1) consisting of one or more compounds each selected from at least two of the above.
Copolymer (A-2-2) consisting of 100 to 10% by weight and one or more compounds each selected from at least two of aromatic vinyl compounds, vinyl cyanide compounds, and other polymerizable monomer compounds. Mixture (A-2) with 80 to 201 Lt% of resin composition (4 to 90% by weight)
) 100 parts by weight, plasticizer 0, 25 P k acrylonitrile-styrene (weight ratio 30 nia 0) copolymer 0.7
5 I created 20 by dissolving it into Ashichiton 10- with ji.
Plasticizer Q3 whose light i transmittance of μ film is 70% or more
) A thermoplastic resin composition comprising 0.5 to 20 parts by weight. 2) Plasticizer (119 is selected from ester type oTffl agent of dicarboxylic acid and monohydric or dihydric alcohol, phosphoric acid ester plasticizer, and epoxy type plasticizer, and 1 type is selected from 2 or more plasticizers. Thermoplastic 41 fat composition according to claim 1. 3) The dicarboxylic acid is heptalic acid, adipic acid, sebacic acid, azelaic acid, maleic acid, fumaric acid, trimellitic acid, citric acid, itaconic acid or The thermoplastic resin composition according to claim 2, which is ricinoleic acid.