JPS596252A - polyester resin composition - Google Patents

Abstract

PURPOSE:To provide a flame-retardant polyester resin compsn. which does not corrode metal, by blending a benzotriazole compd. with a halogen-contg. polyester resin. CONSTITUTION:0.01-5pts.wt. benzotriazole compd. (A) of formula I (wherein R<1>, R<2> are each H, a 1-10C alkyl; Y is H, halogen) such as 2-(2'-hydroxy-5'- methylphenyl)benzotriazole is blended with 100pts.wt. halogen-contg. polyester resin (B). Pref. component B is a copolymer obtd. from terephthalic acid or its ester-forming derivative, a 2-10C alkylene glycol or its ester-forming derivative and an arom. halogen-contg. diol of formula II wherein R3, R4 are each a 2- 4C alkylene; X is halogen; l, m are each 1-4; p, q are each 1-10.

Description

[Detailed description of the invention] The present invention relates to polyester resin compositions.

Specifically, the present invention relates to a polyester resin composition that is flame retardant and does not corrode metals.

The flame-retardant polyester resin composition includes a halogen-containing copolyester resin, for example, terephthalic acid or its ester-forming M 4 form, an alkylene glycol or an ester-forming derivative of alkylene glycol, and a halogen-containing aroma. A copolymerized polyester resin obtained by copolymerizing with a group diol, a polyester resin composition in which an aromatic halogen flame retardant is blended with a halogen-free polyester resin, or the above halogen-containing copolyester resin. , BoIJ containing aromatic halogen flame retardant
Ester resin compositions and the like are known.

These flame-retardant polyester resin-covered polyester resin compositions have excellent mechanical and electrical properties and are widely used in electrical, electronic parts, and other applications, but because they contain halogen, For example, it has the ability to corrode copper (7ft).For this reason, for example, in electric wire connectors, it corrodes the surface of copper parts, leading to poor contact, or breaking or cutting copper parts or wires. There were other inconveniences.

The present inventors have conducted extensive research to obtain a polyester resin composition with the drawbacks mentioned above, and have found that when compounding a 5jl compound with a halogen-containing polyester 4m resin, the resin has The present invention was completed by discovering that corrosion of metals can be significantly suppressed [1] without compromising physical properties such as flame retardance, mechanical properties, and electrical properties. The purpose of this is to provide a polyester resin composition with a high value, and its gist is to provide a polyester resin containing no-rogen.

(,) General formula (in the formula, R1 and R2 are hydrogen atoms and carbon numbers l to i
It shows the argyl disorder of o, and these may be of the same type or different types. Y represents a hydrogen atom or a halogen atom. ) This is a polyester resin composition containing a benzotriazole compound represented by:

Hereinafter, the present invention will be explained in detail.

The halogen-containing 1 polyester resin used in the present invention is striped, halogen-containing copolyester resin, alloy (・E), halogen-free polyester resin or the above halogen-containing copolyester resin with aromatic halogen-based M
Can you give me one that contains 4 fuels?

The halogen-containing copolyester resin is terephthalic acid or its ester-forming derivative.

It is a copolymer of an alkylene glycol compound having 2 to IQ carbon atoms, an ester-forming derivative thereof, and a halogen-containing aromatic diol.

The prephthalic acid may also contain as much as 30 moles of other polysalt waste, such as phthalic acid, inophthalic acid, naphthalene dicarboxylic acid, adipic acid, sebacic acid, trimellitic acid. In addition, as its ester-forming derivative, fl, dimethyl terephthalate J: Unajij31
Can you name 12 alkyl esters?

jA cumulative m2~IO alkylene glycols include ethylene glycol, /, 3-propanediol, /, 4
-butanol, /, 6-hexanediol, /, 1
0-Tekanjimer etc. are listed, and these)
70 mol% or more of glycerin, intererythritol C
2) may also contain a polyhydroxy compound such as.

Furthermore, examples of the ester-forming derivative include ethylene oxide.

The halogen-containing aromatic diol has the general formula (wherein R3 and R4 are alkylene groups having 2 to 4 carbon atoms,
rogen atoms, l and m are /~q, p and q are /
Indicates the number of ~/θ. ), e.g.
L' 7 i'-'F''/ M, produced by the chlorhydrin reaction.

Usually, the above general formula rll)rro & JroR3 and R4
is odoriferous or chlorine, σ) is preferable, specifically, 1,2-his[4-(2-hydroxyethoxy)
-a, s -sifromphenyl]furono(n, ko, J-
Bis[tt-(S-hydroxyethoxy)-,7,! i
-Dichlorophenyl] 20 Roban 1. ), 2-bis[gu(2-hydroxyalkyl)-,7,,5-dibrotophenyl-1propano,co,2-bis[gu(3-hydroxyfurrJboxy)-3,! ;-Sifurono\phenyl]flopane 1.2. ．． 2-His [Goo (3-Hitoroki 7 Sor Pokin) -,? ,,1-dichloropheniha]furopane,co,+7-bis[q-(cohydrojetoxy)-3-fromphenyl1f'1pan,no,hubis[tt-(,2-humanOki'J T-toki 'i)
-),,3. ! ,, 4-Tetrabromphenyl]propane/[What, b, get kicked out.

Polymerized polyester, l+'il Jlt'f, is formed into a mold (1, according to the conventional method for producing polyester, for example, When replacing Nisdel, we prepared the ingredients of the Seven Records,
Method for carrying out subsequent polycondensation reaction, Aroige, Araka U W
) Phthalic acid or an ester-forming derivative thereof is reacted with an alkylene glycol or an ester-forming derivative thereof to produce a low polymer of bishydroxyalkyl terephthalate. If the compound represented by the general formula [11] is added (7) and an aromatic diol is added (7), a polycondensation reaction can be carried out.

During copolymerization, 141 is used to form a copolymerized polynisdel! i,,l 1ltfσ) Halogen-containing': ++F, 3-75% weight, good: F L <
+, ts~/Q, ilj iA If the amount of halogen-containing fabric in the copolymerized polyester resin is too low, the resistance and flammability will be insufficient, and conversely, the resistance will be lower.
L. If you try to do this, it is not desirable because it will impair the mechanical properties.

The halogen-free polyester + i'lJ resin is produced by combining the above-mentioned prephthalic acid or its ester-forming derivative and the carbon class 2-10 alkylenoglycol or its ester-forming derivative, using conventional methods for producing polyester resins. It is a polymer obtained by polycondensation according to the method, and typical examples include polyethylene terephthalate and polyphthylene terephthalate.

Examples of aromatic halogen-based miscellaneous combustion agents include hexabrombenzene, pentafromtoluene (7) J: ') nahaloken-1, tetrabrom diphenyl, decafrom diphenyl, tetrabrom diphenyl ether,
Decabrom diphenyl ether, f caf'rom diphenyl sulfone halogen diphenyls, co, nibis(q-hydroxy-3,S-cyfuromphenyl)propane (tetrabromo bisphenol A), co, corbis(cucrisitoxy-3,S) -dibromphenyl)propane and its low fft properties (2), 2-bis(<=-hydroxyethoxy, ?, j-dibromphenyl)propane, /, 2.2-bis(q-acetoxyphenyl)propane, polycarbonate oligomer of tetrabromobisphenol A, halogenated bisphenol A-j Takeso derivatives, tetrabromophthalic anhydride, tribromophenol condensate, polypentabromobenzyl Examples include acrylate, bromohybristyrene, and a condensate of tetrabromobisphenol, cyanuric acid, and tribromophenol.

This JL Rafang? F group: 1 piece per month of rogen-based pheasant combustion,
Halogen-containing polyester 4174 blended with this The halogen content of the fat is t-is, @*%, and J
-/') Should it be set to 11?

If this ridge is less than 4F, 1, there will not be enough line/fire r+, and on the other hand, if there is too much, it will become 41 (Iso) 11 (41).

Specifically, the benzotriazole compound proboscis that is expressed in the forefoot general formula [1] is t'! , 2(2J-
Hydroxy-5'-methylphenyl)penztriazole (e.g., manufactured by Cibakaikyi Co., Ltd., trade name, Tinuvin P),
Ni(,2'-hydroxy-,?1.,T'-di111
3-butylphenyl) benzotriazole (the same, Tinuvin 3.70), ni(2'-hydroxy-J'-tert-butyl-9'-methylphenyl) benzotriazole (the same,
tenubin32&), co(xl-hydroxy-J', !
'-di-tert-butylphenyl)-S-chloroben7')
IJ A: /'-ru (same, Tinubin 327), no (
2'-Hydroxy-,3',3'-di-aryoamyl phenyl)benzotriazole (32 g Tinuvin), No(,2'-Human IJ Gycy J'-98E amyl-31
-Methylphenyl) to/sotriazole (times, Tinuvin 33;0), J (yJ-hydroxy-5'-octylphenyl)benzotriazole (American Cyanamitsu Co., Ltd. V!, Qushin, -Reiasorb UV-5tt
lt) etc.7. ,).

1111 combination of penztriazole compound: nθ for the halogen-containing 1 polynisder camellia 1 fat 100 tonne sample
/ ~ 5 tons i, % part, Yoshii or o, 05 ~ 3 parts 8
If the degree is too much, the effect of preventing metal corrosion will be sufficient. 1'C.

Various known methods can be used as a method for blending the halogen-containing polyvarnish/Furuju'IW'F benzotriazole compound. Mu'+ Extrusion J
You should be able to tell me how to melt and knead materials such as z, t, Bunbury mi, j゛-1j-, etc. every month and make them into pellets.

The polyester 1υ: Ili+ 4i+ composition of the present invention may be mixed with acids (refractory auxiliaries such as 1-anFJ or phosphorus), glass nano 1ml (carbon fiber, asbestos, etc.) depending on the purpose. Reinforcing agents, silica, alumina, and alumina.

Silica magnesia, Kuf I:l+7 calcium, calcium carbonate, crow beads, crow flakes, and other photochemicals, fungal beds! C7it agent, paraffin wax σ) JX') 7': C7it agent, ZONOL+! It may also contain well-known additives such as 511 shavings, can-preventing agents, dyes and pigments.

The composition of the present invention S1 has excellent viscosity properties such as flammability, mechanical properties, and electrical properties, and is suitable for corrosion of metals, especially swords! l1l-Since there is no rotor, its value as an engineering plastic ((+'j is extremely C dog-like, injection,
Various molding methods such as extrusion, blowing, and compression IC, J1. Therefore, various three-dimensional molded products, various containers, films, sheets, and other molded products of various shapes. However, the present invention is not limited to the following examples unless it departs from the gist of the invention.

In addition, in the fi KQ example, r ) 31S J and "%" respectively indicate "Tsumekobu" k and "Shigekami circulation".

In addition, the flammability is UL-9II (Underwrite).
er's Lah-nratorle++, Tnc
, ) The results of the standard vertical combustion test are shown, and the results of the gold 10,000 corrosion test are the values measured using the following method.

A glass test tube with an α diameter of 30 mm and a length of 20 θ is filled with a polyester resin composition of a proboscis pellet lOθ2,
A copper plate of fir 20 mm, width o mm, and thickness 2 M was hung vertically so that its F side was 1 mm from the top surface of the pellet-packed bed, and the air flow was in a narrow state. 2
After being left at 0'C for 3 hours, the surface of the copper plate from the lower side to lo- was treated with the color 1. lf
The L value was measured using 1 Color Difference i1''1' C-, SD type manufactured by Nippon Steel Co., Ltd. The larger the L value, the brighter the surface and the less corrosion.

Example 1-2 and Comparative Example 7 - Copole I! Melting point obtained by polymerizing 700 parts of polybutylene terephthalate (manufactured by Mitsubishi Kosei Kogyo, trademark, Novadur Sθ20) with a viscosity of /2 and pentabromobenzyl acrylate in a propylene glycol solvent using hibenzoyl peroxide as a catalyst /θS ~ //θ°C, 1 part of polypentabromobenzyl acrylate with a from content of 70 g, 1 part of antimony trioxide, and 2-g parts of antimony trioxide in the amounts shown in Table 1 below.
(,2'-Hydroxy-1-methylphenyl)benzotriazole (manufactured by Ciba-Kygyi, trademark, Tenubin P
), and mix the II OJulφ extruder (Isuzu Kakoki■
The mixture was melt-kneaded and extruded into pellets at 200° C. using the following methods:

This pellet was used to conduct the above-mentioned metal Temperature, 2 A OC.

Injection molding was carried out at a mold temperature of gO°C, an injection time of 70 seconds, and a cooling time of 20 seconds.

The results of the metal mold corrosion test and the flammability of the molded article were as shown in Table 1 below. In addition, tTiil before joint corrosion test
The L value of the plate surface was 37.0.

Also, because of the specific axis, Co(2'-hydroxy-1ri'-
When methylphenyl)penzotriazole was not blended, and in place of J-(2'-hydroxy-5r-methylphenyl)benzotriazole, p-ntaerythritol tetrakis(q-hydroxy-3,S- The results of the case where propionode (manufactured by Ciba Geigy, trademark, Irganox 1O7O) was blended are also shown.

Table 1 Reference Examples Pellets of polyph J-lenderephthalate used in Example 1 and a solution of 0.5 parts of polybutylene terephthalate tooHrc2-(u'-hydroxy-51-methylphenyl)benzotriazole were mixed together. 11.d was conducted on the pellets prepared using metal scraps n17), and the L value was ? &,! and 3ri6. It's sweet, ``6 sex is both and 4 +' (I
Hello, Ivy.

μ廁4'yll 3-q〕(Yu・'Kobii IIi')
'(kll 3 dimethyl phthalate/θo>”:
:1. /, 65 parts of 4t-butanediol, and 2.2
Copolymerization of 1 part of -bis(<=-(2- to 1.Jxy-3,5-duglomphenyl))propane W''C obtained intrinsic viscosity θgs, halogen-containing copolymerization with frome content of 1% Polynisder resin / t) θ1 (15, antimony triacid, tribromophenol Is compound (Versicol Co., Ltd.-1p-VCC9,75) / u part, and the following amount, 2:lf, 1 of 2 shown in -(2'-hydroxy-
&'-methylphenyl)benzotriazole was mixed and melt-kneaded in a bath in the same manner as in Example 1 to form pellets.

A metal corrosion test was conducted using this pot, and a test piece was formed into a test piece.

The results of the gold dust corrosion test and flammability were as shown in Table 1 above. In addition, L on the surface of the copper plate of test FA Ail
The value was 370.

In addition, for comparison 0), a substitute for co-(2'-hydroxy-5'-methylphenyl)benzotriazole was added, and a substitute for 2-(2'-hydroxy-5'-methylphenyl)benzotriazole. Please also record the results when pentaerythritol trakis(terhydroxy-3,S-di-tert-butylphenyl)globionate O, S parts were blended t7.

ㅅ“132 tables Applicant: Mitsubishi Kasei Kobo Co., Ltd. Agent, Patent Attorney, For De-bath - (Number, number)

Claims (1)

Scope of Claims (1) A halogen-containing polynisder resin having the general formula (wherein R1 and R2 represent a water cumulative atomic size or an alkyl group having 1 to 10 carbon atoms, and these are benzotriazoles represented by the same type) A polyester resin composition formed by blending a compound. (2) The halogen-containing polynisder resin contains: (1) terephthalic acid or an ester-forming derivative thereof, (2) an alkylene glycol having up to 10 carbon atoms or an ester-forming derivative thereof, and (2) the general formula (In the formula, R3 and R4 are alkylene groups having 2 to 5 carbon atoms, X is a halogen atom, ! and m are numbers of /-9, and p and q are numbers of /-10.) A polyester resin composition according to Claim No. (1) Jg, which is a halogen-containing copolymer polyester resin obtained by copolymerizing an aromatic diol. The polyester resin composition according to range (1). (4) The blending ratio of the benzotriazole compound is...0.01 to 0.01 parts by weight of the rogen-containing polyester resin lθθ
The polyester resin composition according to claims (1) to (3), which is a polyester resin composition.