JPH115967A - Antistatic agent for resin, resin composition, and molded item produced by molding the composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain an antistatic agent that is efficiently concentrated on the surface of a resin compsn. and exhibits an excellent antistatic function at a low concn. by constituting the antistatic agent of a copolymer formed from a polymerizable monomer having a hydrophilic or conductive group, a fluorinated polymerizable monomer, and another polymerizable monomer which, when homopolymerized, gives a homopolymer compatible with a resin. SOLUTION: This agent is a copolymer comprising polymn. units (A) derived from a polymerizable monomer (e.g. polyethylene glycol monomethacrylate) having a hydrophilic or conductive group pref. in a content of 5-90 wt.%, polymn. units (B) other than units a and derived from a fluorinated polymerizable monomer (e.g. a perfluoroalkylethyl acrylate having, on average, 9 carbon atoms) pref. in a content of 1-57 wt.%, and polymn. units (C) other than foregoing polymn. units and derived from a polymerizable monomer (e.g. methyl methacrylate) which, when homopolymerized, gives a homopolymer compatible with a resin, pref. in an amt. of 4-86 wt.%.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to an antistatic agent for a resin having excellent antistatic properties, a resin composition containing the same, and a molded article obtained by molding the resin composition.

[0002]

2. Description of the Related Art In general, a resin has a high electrical insulation property and is easily charged with static electricity, so that it is easy to absorb dust. In a factory or the like, static electricity is generated and accumulated, which hinders the operation, and there is a possibility that a fire may occur due to spark discharge. In addition, there is also a problem that a human body that comes into contact with the molded resin product receives an electric shock due to contact with the grounding body and feels uncomfortable.

For this reason, various studies have been made on the prevention of electrification of resins. For example, there is a method in which carbon black or metal powder is blended with the resin. In this case, however, the molded product becomes opaque and a desired beautiful color cannot be expressed, so that there is a disadvantage that the range of use is limited.

[0004]

Therefore, it has been studied to incorporate an antistatic agent comprising an organic compound into a resin.
Various organic compounds have been proposed, but molded products obtained using these antistatic agents may cause the antistatic agent to bleed out to the surface over time, causing stickiness and surface contamination. However, there is a defect that the durability of the antistatic property is poor. Attempts have been made to make the surface hydrophilic by adding a graft copolymer of a methyl methacrylate macromonomer and a hydrophilic monomer (Yamashita et al., Industrial Materials, 3346 (1985)). is not.

The present invention has been made in view of the above circumstances, and provides an antistatic agent having excellent chargeability and a resin composition containing the same. The resin composition maintains various properties of the resin, has excellent antistatic properties, and can be formed into a molded product excellent in heat resistance (aging), weather resistance and bleed resistance.

[0006]

The present inventors have studied to solve the above-mentioned various problems, and as a result, have found that three specific polymer units, that is, polymer units containing a hydrophilic or conductive group. When a copolymer containing three polymerizable units having surface transferability and a polymerizable unit having compatibility with the resin as essential polymerizable units is blended with the resin to form a composition, the surface of the resin composition becomes hydrophilic on the surface of the resin composition. It has been found that a group having a property or conductivity can be concentrated, and an excellent antistatic ability is exhibited.

Further, since the above-mentioned copolymer exhibits a stable anchor effect derived from polymerized units having compatibility with the resin, a concentrated antistatic group is stably present on the sheet surface, and the bleed resistance is reduced. It is possible to provide a molded article having an excellent out-out property and having a long lasting antistatic ability.

That is, the present invention provides the following polymerized unit (b)
¹ ), the following polymerized unit (b ² ), and the following polymerized unit (b
³ ) an antistatic agent for a resin comprising a copolymer (B) containing
And a resin composition containing the resin antistatic agent, and a molded article obtained by molding the resin composition. Polymerized unit (b ¹ ): a polymerized unit based on a polymerizable monomer having a hydrophilic or conductive group. Polymerized unit (b ² ): a polymerized unit based on a polymerizable monomer containing a fluorine atom, and a polymerized unit other than the polymerized unit (b ¹ ). Polymerized unit (b ³ ): a polymerized unit based on a polymerizable monomer having compatibility with a resin when a homopolymer is used, and other than the polymerized unit (b ¹ ) and the polymerized unit (b ² ) Polymerized units.

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION The copolymer (B) comprises three specific structural units, namely, a polymerized unit (b ¹ ) and a polymerized unit (b).
² ) and a copolymer containing a polymerized unit (b ³ ).
Hereinafter, each structural unit will be described in order.

The polymerized unit (b ¹ ) is a polymerizable monomer containing a hydrophilic or conductive group [hereinafter referred to as monomer (b)
¹ ). ].

As the monomer (b ¹ ), a compound represented by the following formula 1 is preferable. DQ ¹ -U ¹ Formula 1 wherein the symbols in the formula have the following meanings. D: polymerizable unsaturated group. Q ¹ : a single bond or a divalent linking group. U ¹ : a monovalent group having hydrophilicity or conductivity.

As the polymerizable unsaturated group (D) in the formula 1, at least one of a vinyl group and a hydrogen atom in these groups is a halogen atom (a chlorine atom, a fluorine atom, etc.) or a lower alkyl group (a methyl group). And the like).

When Q ¹ is a divalent linking group, -CO
O (CH _{2) m} - (provided that, m is an integer of _{0~4.), - (CH 2} ) m - ( provided that, m is an integer of 2-4.), Or, - (CH ₂ ) _P -P ^h- (CH
_{2) q} -. (However, p, q are each an integer of 0 to 4, P ^h is showing a 1,4-phenylene group).

A hydrophilic or conductive monovalent group (U
^{As 1} ), a residue having hydrophilicity and conductivity present in various organic compounds known as an antistatic agent is suitable, and a nonionic compound, an anionic compound, a cationic compound, or an amphoteric compound is suitable. Examples include a monovalent group obtained by removing one hydrogen atom from a known antistatic compound known as a system compound. Examples of the antistatic compound include the following.

Nonionic compounds polyoxyethylene-alkylamine, polyoxyethylene-alkylamide, polyoxyethylene glycol alkyl ether, polyoxyethylene glycol alkylphenyl ether, glycerin fatty acid ester, sorbitan fatty acid ester, and glycerin monoester phosphate , Stearyl diethanolamine, etc.

Anionic compounds alkyl sulfonate, alkyl benzene sulfonate, R ¹⁰ SO ₃ Na, alkyl sulfate, R ¹¹ O
SO ₃ Na, alkyl phosphate, R ¹² OPO ₃ K
₂ , polyphosphate, pentaalkyltripolyphosphate, and the like (provided that R ¹⁰ , R ¹¹ , and R ¹² each represent an alkyl group).

A quaternary ammonium salt such as ammonium chloride, ammonium sulfate, ammonium nitrate, an alkylamine salt, a higher amine ethylene oxide adduct,
Quaternary phosphonium salts and the like.

Amphiphilic compounds Aminocarboxylic acid derivatives such as betaines, metal salts of alanine-type amphoteric surfactants, metal salts of imidazoline-type amphoteric surfactants, metal salts of diamine-type amphoteric surfactants, containing oxyethylene groups Metal salts of amphoteric surfactants and the like can be mentioned.

As the monomer (b ¹ ), a polymerizable group such as an acryloyl group, a methacryloyl group, or a vinyl group is bonded to a monovalent group obtained by removing one hydrogen atom from the above compound known as an antistatic agent. The polymerized monomer represented by the following formula 3 is particularly preferred. CH ₂ = CR ¹ COO-U ² Formula 3 where the symbols in the formula have the following meanings. R ¹ : hydrogen atom or methyl group. U ² : a monovalent group obtained by removing one hydrogen atom from a nonionic compound, anionic compound, cationic compound or amphoteric compound. As specific examples of U ² , the groups described for U ¹ in Formula 1 can be employed.

The monomer (b)¹ The following compounds are preferred as
Good. Where R in the following formula ¹³, R¹⁴Each
Represents an alkyl group having 1 to 6 carbon atoms, and is a linear alkyl group.
Groups are preferred. R^FifteenRepresents a hydrogen atom or a methyl group
You. X represents a halogen atom, preferably a chlorine atom.
n and m each represent an integer of 1 or more. P^h Is 1,
Shows a 4-phenylene group.

[0021] ^{_{CH 2 = CR 1 COOCH 2 CH}} (OH) CH 2 N + (R 13) 3 · X - CH 2 = CR 1 COOCH 2 CH 2 P + (R 14) 3 · X - CH 2 = CR 1 -P ^h -CH ₂ P ⁺ (R ¹⁴ ) ₃・ X ^- CH ₂ = CR ¹ -COOP ⁺ (R ¹⁴ ) ₃・ X ^- CH ₂ = CR ¹ COO (CH ₂ CH ₂ O) _n R ¹⁵ CH ₂ = CR ¹ COO [CH ₂ CH (CH ₃ ) O] _m R ¹⁵ CH ₂ = CR ¹ COO (CH ₂ CH ₂ O) _n [CH ₂ CH (CH ₃ ) O] _m R ¹⁵ CH ₂ = CR ¹ COOCH ^{_{2 CH 2 N + (CH 3}} ) CH 2 COO -

The polymerized unit (b ² ) is a polymerizable monomer containing a fluorine atom [hereinafter referred to as monomer (b ² )]. And a polymerized unit other than the polymerized unit (b ¹ ). Since the polymerized unit (b ² ) contains a fluorine atom, it is considered to have a function of transferring the copolymer (B) to the surface in the resin composition.

The monomer (b ² ) is preferably a compound having a fluorine-substituted polymerizable unsaturated group such as vinyl fluoride, or a compound having both a fluorine atom-containing group and a polymerizable unsaturated group. . As the fluorine atom-containing group, a polyfluoroalkyl group is preferable.

[0024] In the following, a polyfluoroalkyl group called ^the R ^f group in the molecule compound R ^f group-containing monomer containing a polymerizable unsaturated group as ^the R ^f group (b ²⁾ that. In addition, acrylate and methacrylate are collectively referred to as (meth) acrylate. The same applies to other compounds.

The monomer (b)^Two ) Is R^f Group containing simple substance
Body (b^Two ) Are preferred, for example R ^f Having a group
TA) acrylate, R^f Group-containing vinyl compound, R^f 
Allyl compounds having a group.

A particularly preferred monomer (b ² ) is a (meth) acrylate having an R ^f group represented by the following formula 2. CH ₂ = CR ² COO-Q ² -R ^f Formula 2 where the symbols in the formula have the following meanings. R ² : hydrogen atom or methyl group. Q ² : a single bond or a divalent linking group. R ^f : R ^f group. Q ² in the formula 2 is preferably a divalent organic linking group, particularly preferred are those listed in Examples described later.

The R ^f group is a group in which two or more hydrogen atoms of an alkyl group have been substituted with fluorine atoms. The number of fluorine atoms in the R ^f group is preferably at least (the number of fluorine atoms in the R ^f group)
/ (The number of hydrogen atoms present in the alkyl group having the same carbon number corresponding to the R ^f group)] × 100 (%)
It is preferably at least 0%, particularly preferably at least 80%. An etheric oxygen atom (-O-) may be inserted between the carbon-carbon single bonds of the ^Rf group. For example,
An ^Rf group containing an oxypolyfluoroalkylene moiety such as oxypolyfluoroethylene and oxypolyfluoropropylene is exemplified.

The carbon number of the R ^f group is preferably 1 to 20, more preferably 4 to 16, and particularly preferably 6 to 12. R ^f
The group has a linear or branched structure, and preferably has a linear structure. In the case of a branched structure, it is preferable that the branched portion exists near the terminal of the R ^f group and is a short chain having about 1 to 3 carbon atoms. Further, a chlorine atom may be present at the terminal portion. The structure of the terminal portion of the R ^f group is CF
_{3 -, CF 2 H-, CF} 2 Cl -, (CF 3) 2 CF-
And the like.

The R ^f group in the present invention is preferably a perfluoroalkyl group in which substantially all of the hydrogen atoms of the alkyl group have been replaced by fluorine atoms (hereinafter referred to as R ^F groups). The number of carbon atoms in R ^F group having 1 to 20 is rather preferred, in particular 4 to 16
Is preferred. The R ^F group is an R ^F group having a linear or branched structure.
^F (CF ₂ ) _n- [n is an integer of 4 to 16]
A linear R ^F group represented by is preferable, and one having n of 7 to 13 is particularly preferable. Further, the R ^F group is represented by carbon-
An etheric oxygen atom may be included between carbon bonds.

Specific examples of the R ^f group include, but are not limited to, the following structures. In the following specific examples, groups corresponding to groups having structural isomerism are also included. C ₂ F
_{5 -, C 3 F 7 -} [F (CF 2) 3 -, and (CF
₃₎ includes both ₂ CF-. _{], C 4 F 9 - [} F (CF
_{2) 4 -, (CF 3} ) 2 CFCF 2 -, (CF 3) 3 C
-, CF ₃ CF ₂ CF (CF ₃ )-], C ₅ F ₁₁
-[F (CF ₂ ) _5- , (CF ₃ ) ₂ CF (CF ₂ ) ₂
−, (CF ₃ ) ₃ CCF ₂ −, CF ₃ CF ₂ CF (CF
₃ ) including structurally isomeric groups such as CF _2- ], C ₆ F ₁₃ −
_{[F (CF 2) 3 C} (CF 3) 2 - including structural isomers groups _{such], C 8 F 17 -,} C 10 F 21 -, C 12 F 25 -, C 15
_{F 31 -, HC t F 2t} - (t 1 to 18 integer), (CF
_{3) 2 CFC s F 2s -} (s is an integer from 1 to 15) such as.

CF ₃ (CF ₂ ) ₄ OCF (CF ₃ ) —,
F [CF (CF ₃ ) CF ₂ O] _s CF (CF ₃ ) CF ₂
CF _2- , F [CF (CF ₃ ) CF ₂ O] _t CF (CF
_{3) -, F [CF (} CF 3) CF 2 O] u CF 2 CF 2
−, F (CF ₂ CF ₂ CF ₂ O) _v CF ₂ CF ₂ −, F
_{(CF 2 CF 2 O) w} CF 2 CF 2 -, C 6 F 5 -, C
_{6 F 5 CF = CF-, CH} 2 = CHC 6 F 12 - (s, t
Is an integer of 1 to 10, u is an integer of 2 to 6, v is an integer of 1 to 11, and w is an integer of 1 to 11. )Such.

The (meth) containing R ^f group in the present invention
Examples of the acrylate include the following compounds.
However, the symbols R ² and R ^f in the compound have the same meaning as in Formula 2. _{^{CH 2 = CR 2 COOCH 2 CH}} 2 R f, CH 2 = CR 2 COOCH 2 CH 2 N (C 3 H 7) CO
_{^{R f, CH 2 = CR 2}} COOCH (CH 3) CH 2 R f, CH 2 = CR 2 COOCH 2 CH 2 N (CH 3) SO 2
R ^f , CH ₂ = CR ² COOCH ₂ CH ₂ N (CH ₃ ) COR
_{^{f, CH 2 = CR 2 COOCH}} 2 CH 2 N (C 2 H 5) SO
_{^{2 R f, CH 2 = CR}} 2 COOCH 2 CH 2 N (C 2 H 5) CO
R ^f , CH ₂ = CR ² COOCH ₂ CH ₂ N (C ₃ H ₇ ) SO
₂ R ^f , CH ₂ ＣＲCR ² COOCH (CH ₂ Cl) CH ₂ OCH
₂ CH ₂ N (CH ₃ ) SO ₂ R ^f .

The (meth) compound containing an R ^f group in the present invention
One or more acrylates can be used. 2
When using more than one kind, two or more kinds of compounds having different structures may be used, and two or more kinds of compounds having different carbon numbers of the R ^f group may be used.

The R ^f group-containing monomer (b ²⁾ is of the formula 2 R ^f
Is preferably an R ^F group having 4 to 16 carbon atoms. ^If the carbon number of R ^f in Formula 2 is small, the surface migration in the resin may be insufficient. On the other hand, ^if the carbon number of R ^f is too large, the compatibility between the compound represented by the formula 3 and another monomer may be reduced, and the yield at the time of copolymerization may be reduced. Further, the compatibility with the resin may be reduced, and the surface transferability may be reduced.

The polymerized unit (b ³ ) is a polymerizable monomer (hereinafter, referred to as monomer (b ³ )) which is compatible with a resin when formed into a homopolymer. ]. Also,
The polymerized unit (b ³ ) is a polymerized unit other than the polymerized unit (b ¹ ) and the polymerized unit (b ² ). The monomer (b ³ )
It is considered to have a function as an anchor for the resin.

Generally, the compatibility is determined by the S _p between the polymers.
Value (Solubility parameter), and in order to have compatibility, the difference is -2 to +
2, preferably in the range of -1.5 to +
It is preferably in the range of 1.5. Further, the monomer (b ^3), alone S _p value when the polymer and the can is preferably from 7.5 to 11.5 as an absolute value, in particular 8.
It is preferably from 0 to 11.0.

As the monomer (b ³ ), for example, (meth) acrylate monomers, vinyl ester monomers, vinyl cyanide monomers, aromatic vinyl monomers, Combinations are mentioned, and (meth) acrylate monomers are particularly preferred.

As an example of the (meth) acrylate monomer, an alkyl (meth) acrylate is preferred. The alkyl (meth) acrylate preferably has 1 to 8 carbon atoms in the alkyl group portion.
More preferably those which are 6, in particular (meth) [S _p value = 9.5 homopolymers] methyl acrylate, (meth) acrylate, (meth) S _p of butyl acrylate [homopolymer Value = 8.6].

Examples of the vinyl ester monomer include vinyl acetate, vinyl propionate, vinyl butyrate and the like. Examples of the vinyl cyanide monomer include acrylonitrile, methacrylonitrile and the like. Examples of the aromatic vinyl monomer include α-methylstyrene, vinyltoluene, chlorostyrene and the like.

The copolymer (B) of the present invention is a polymerized unit other than the above polymerized units (b ¹ ), (b ² ) and (b ³ ) [hereinafter referred to as other polymerized unit. ] May be included.
As other polymerization units, monomers other than monomers (b ¹ ) to (b ³ ) [hereinafter referred to as other monomers]. ] Is preferred.

Examples of other monomers include ethylene, vinyl acetate, styrene, p-methylstyrene, vinyl alkyl ether, and alkyl (meth) acrylate having an alkyl group having 9 or more carbon atoms. When polymerized units based on other monomers are included, the copolymer (B)
The content is preferably 30% by weight or less, particularly 0% by weight.
It is preferred to be more than 10% by weight.

The structure of the copolymer (B) of the present invention is a copolymer containing the above-mentioned polymerized units (b ¹ ) to (b ³ ). The chain structure of the copolymer (B) may be any of graft, block and random, but is preferably a random copolymer. In a graft polymer or a block polymer, only a fluorine atom is concentrated on an extremely surface, and a hydrophilic and conductive group is not exposed on the surface, and the antistatic property is reduced.

The proportion of the polymerized unit (b ¹ ) in the copolymer (B) is preferably from 5 to 90% by weight. If the proportion of the polymerized unit (b ¹ ) exceeds 90% by weight, the proportions of the polymerized unit (b ² ) and the polymerized unit (b ³ ) become relatively small, and thus the surface migration in the resin may be reduced. is there. When the proportion of the polymerized unit (b ¹ ) is less than 5% by weight, the antistatic performance of the resin becomes insufficient, and the addition of a large amount of an antistatic agent may deteriorate the physical properties of the resin.

The proportion of the polymerized unit (b ² ) in the copolymer (B) is from 10 to 60% by weight of the portion of the copolymer (B) excluding the polymerized unit (b ¹ ) [that is, the copolymer (B ² )]. Polymer (B)
1 to 57% by weight], and particularly preferably 30 to 40% by weight [that is, 3-38% by weight in the copolymer (B)].

When the proportion of the polymerized unit (b ² ) in the copolymer (B) is less than 1% by weight, the fluorine content in the copolymer (B) is reduced, and the surface transferability derived from fluorine atoms is exhibited. However, the concentration of the copolymer (B) in the vicinity of the resin surface may not be sufficient. If the proportion of the polymerized unit (b ² ) exceeds 57% by weight, the compatibility of the copolymer (B) with the resin is too high, and the surface transferability is reduced. Concentration may decrease.

The proportion of the polymerized unit (b ³ ) in the copolymer (B) is from 40 to 90% by weight of the portion of the copolymer (B) excluding the polymerized unit (b ¹ ) [ie, Polymer (B)
4 to 86% by weight], particularly 60 to 70% by weight [that is, 24 to 67% by weight in the copolymer (B)].
Is preferred.

The method for synthesizing the copolymer (B) is not particularly limited, and any known or well-known copolymerization method can be employed.

For example, the monomers (b ¹ ) to (b ³ ) and, if necessary, other monomers are converted to radicals such as azobisisobutyronitrile (hereinafter referred to as AIBN) and benzoyl peroxide. Examples of the method include suspension polymerization, emulsion polymerization, and solution polymerization using an initiator. Solutions used for solution polymerization include toluene and tetrahydrofuran (hereinafter, referred to as
THF), acetone, hydrochlorofluorocarbon (HCFC-225ca, HCFC-225cb)
And the like.

The number average molecular weight _Mn of the copolymer (B) is 50
00 to 30000 is preferred. If _Mn is less than 5,000, the anchor effect on the resin may be insufficient, and if _Mn is more than 30,000, the mobility of the molecules may be low and the concentration on the surface may be insufficient.

The resin antistatic agent of the present invention comprising the copolymer (B) imparts hydrophilicity or conductivity to the resin by being incorporated into the resin to form a resin composition. It is not particularly limited as long as it is a resin of the copolymer (B) and compatibility as a resin, being in the copolymer (B) within the range difference of + 2-2 S _p value and are preferred. For example, a polyurethane resin, a vinyl chloride resin, a silicone resin, an acrylic resin, or an epoxy resin is preferable. The amount of the copolymer (B) in the resin composition is preferably from 0.1 to 40% by weight in the resin composition, and particularly preferably from 0.1 to 30% by weight. If the amount is less than 0.1% by weight, desired surface properties may not be obtained. If the amount exceeds 40% by weight, physical properties of the resin may be reduced.

It is particularly preferred that the copolymer (B) of the present invention is contained in a vinyl chloride resin to form a vinyl chloride resin composition. Examples of the vinyl chloride resin, vinyl chloride copolymers (Sp value = 9.5), vinyl chloride - (about S _p value = 9.9) vinyl acetate copolymer, vinyl chloride - acrylate copolymerization Copolymer, vinyl chloride-vinylidene chloride copolymer, vinyl chloride-ethylene copolymer ( _Sp value = 9.
1) and the like, and these may be used alone or in combination of two or more. Vinyl chloride resin in the present invention,
That S _p value is in the range of 9-10 is preferred. The average degree of polymerization of the vinyl chloride resin is preferably from 600 to 350.
0, more preferably in the range of 800 to 2500. If the average degree of polymerization is too small, the weather resistance of the resin itself may be reduced, and mechanical properties such as impact resistance and elastic modulus, and thermal stability may be reduced. If the average polymerization degree is too large, the moldability may be reduced.

The resin composition of the present invention may contain other additives. As other additives that can be included in the resin composition of the present invention, antioxidants, heat stabilizers, lubricants, and plasticizers are preferable, and, if necessary, an ultraviolet absorber, a light stabilizer, a pigment, and an antistatic agent. Agents, flame retardants, flame retardant auxiliaries, and the like.

Examples of other additives include organic tin heat stabilizers such as dibutyltin dilaurate and dibutyltin malate;
Aliphatic carboxylate salts such as calcium stearate and zinc stearate, Ba-Zn based inorganic stabilizers, epoxy compounds such as epoxidized soybean oil, stabilizers such as organic phosphates,
MBS (copolymer of methyl methacrylate, butadiene and styrene), impact modifiers such as acrylic silicone, lubricants such as higher fatty acids, phenolic antioxidants, fillers such as carbon black, silica, calcium carbonate, etc. .

In addition, as long as the effects of the present invention are not impaired, inorganic flame retardants such as titanium phosphate, aluminum hydroxide and magnesium hydroxide, 2,5,6-tetrachloroisophthalonitrile, 10,10 ′ -A fungicide such as oxybisphenoxyarsine, and a coloring agent such as phthalocyanine blue, phthalocyanine green, alizarin lake, zinc white, and carbon black can be included.
In addition, compounds other than those exemplified here may be included as necessary.

When the resin composition of the present invention is a vinyl chloride resin composition containing a vinyl chloride resin and an antistatic agent, even if it is a soft vinyl chloride resin containing a plasticizer,
A hard vinyl chloride resin containing no plasticizer may be used. As the plasticizer used for the soft vinyl chloride-based resin, those generally used can be employed. Examples of the plasticizer include the following compounds. One or more of these plasticizers can be used.

Phthalate ester plasticizers such as dibutyl phthalate, diethyl phthalate, diheptyl phthalate, bis-2-ethylhexyl phthalate, di-n-octyl phthalate, dinonyl phthalate, diisodecyl phthalate, ditridecyl phthalate and butyl benzyl phthalate .

Dimethyl adipate, diisobutyl adipate, dibutyl adipate, bis-2-ethylhexyl adipate, diisodecyl adipate, dibutylene glycol adipate, bis-2-ethylhexyl azelate, dimethyl sebacate, dibutyl sebacate, bis-
Aliphatic dibasic acid esters such as 2-ethylhexyl sebacate;

Epoxy compounds such as epoxidized soybean oil and octyl epoxy stearate. Trimethyl phosphate, triethyl phosphate, tributyl phosphate, tris-2-ethylhexyl phosphate, tributoxyethyl phosphate, trioleyl phosphate, triphenyl phosphate, tricresyl phosphate, trixylenyl phosphate, cresyl diphenyl phosphate, xylendiphenyl phosphate,
Phosphate ester plasticizers such as 2-ethylhexyl diphenyl phosphate.

2-methyl-1,8-octanediol,
1,2-propanediol, 1,3-butanediol,
Ester plasticizers such as esters of hydroxy compounds such as 2-ethylhexanol and n-octanol with adipic acid. Trimellitic acid-based plasticizers such as tris (2-ethylhexyl) trimellilate and tri (isodecyl) trimellilate. In addition, pyromellitic acid compounds such as 2-ethylhexyl pyromellilate and biphenyltetracarboxylic acid ester plasticizers.

The resin composition of the present invention can be molded into various molded articles. Examples of the method for molding the resin composition include methods such as injection molding, extrusion molding, press molding, and calendar molding, which are general methods applied to thermoplastic resins. It is preferable that the resin composition is formed after being formed into pellets or powder. Pellets can be made with a conventional extruder. Extrusion conditions may be any as long as the resin does not deteriorate, and the shape of the screw, the extrusion temperature, the extrusion speed, and the like are not particularly limited. Regarding molding conditions,
The conditions in a normal molding machine can be adopted, and the screw shape, injection temperature, speed, pressure, and the like are not particularly limited as long as the resin does not deteriorate.

The resin composition of the present invention can be molded into various forms of molded articles in which advantageous effects due to antistatic performance can be expected. Examples of the molded body include a member for an automobile interior, a member for a building material such as an interior material and a wallpaper, and the like.

[0062]

EXAMPLES The polymerizable monomers, polymerization solvents, reprecipitation solvents, and radical initiators used in the examples were all unpurified. Various measurements were performed under the following conditions.

(1) Number average molecular weight, molecular weight distribution Number average molecular weight M _n and molecular weight distribution M _w / M _n were measured by gel permeation chromatography [HLC802 manufactured by Tosoh Corporation].
0] under the following conditions. Column: TSK gel column manufactured by Tosoh Corporation. Detectors: UV and RI. Eluent: THF. Flow rate: 1.0 ml / min. Temperature: 40 ° C. Reference substance: styrene. (2) ¹ H-NMR Measurement was performed at room temperature using CDCl ₃ as a heavy solvent. TMS was used as a reference material.

[Synthesis Example of Vinyl Chloride Resin (A)] 3 g of partially saponified polyvinyl alcohol (manufactured by Nippon Synthetic Chemical Company, trade name: Gohsenol KH-20), AIBN 0.34
1 g of ion-exchanged water and 1170 g of ion-exchanged water were added to the pressurized reactor, and after purging with nitrogen gas, 300 g of vinyl chloride monomer was charged. After reacting at 65 ° C. for 6 hours, unreacted monomers were recovered. Next, dehydration and drying were performed to obtain 285 g of a powdery vinyl chloride resin. The polymerization degree of the obtained vinyl chloride resin was 1,300. Hereinafter, this polymer is referred to as polymer A.

[0065] [Synthesis Example 1: Copolymer B ¹ of Synthesis internal glass flask 1 liter with nitrogen, perfluoroalkylethyl acrylate average carbon number of the R ^F group is a 9 [CH ₂ = CHCOOCH ₂ CH ₂ R ^F , hereinafter referred to as FA] 100 g, methyl methacrylate (hereinafter, referred to as MMA) 200 g, polyethylene glycol monomethacrylate (manufactured by NOF Corporation, trade name: Blenmer PE, hereinafter, referred to as PE) 300 g, AIBN 5.0
g of toluene and 2500 g of toluene were reacted at 60 ° C. for 8 hours. After cooling the flask, the content was poured into methanol to obtain a copolymer. _Mn of the obtained copolymer is 10
000, _Mw / _Mn was 1.86. ¹ H-NMR
As a result of obtaining the composition ratio of the copolymer, FA / MMA / 4
MA = 98/205/297 (weight ratio). Hereinafter, this copolymer as the polymer B ^1.

[Synthesis Examples 2 to 10: Synthesis of Copolymers B ^{2 to} B ¹⁰ , Comparative Synthesis Examples 1 and 2: Synthesis of Copolymers C ^{1 and} C ² ]
The types and amounts (unit: g) shown in Tables 1 to 3 were charged with a polymerizable monomer, a polymerization initiator, and 2500 g of toluene.
Under the same conditions as in Synthesis Example 1, copolymers B ^{1 to} B ¹⁰ and C ^{1 to} C ^10
2 was synthesized. Tables 1 to 3 show M _n and the composition ratio (unit: weight ratio) of the obtained copolymer. However, in Tables 1 to 3, butyl acrylate is represented by BA, and methacrylic acid [(2-hydroxy-3-trimethylammonium) propyl] chloride (trade name: Blenmer QA, manufactured by NOF Corporation) is represented by Q.
A, tri-n-butyl (4-vinylbenzyl) phosphonium chloride (manufactured by Nippon Chemical Industry Co., Ltd .: trade name: Cydaps 4CMS) 4CMS, methacrylic acid [2- (tri-
n-butylphosphonium) ethyl] chloride (manufactured by Nippon Chemical Industry Co., Ltd., trade name: Cydaps 4MA) as 4MA,
(4-Vinylphenyl) sulfonic acid was abbreviated as StNa.

[0067]

[Table 1]

[0068]

[Table 2]

[0069]

[Table 3]

[Examples of Preparation of Test Pieces 1 to 20] The vinyl chloride polymer A obtained above and dioctyl phthalate (hereinafter referred to as DO)
P) and copolymers B ^{1 to} B ¹⁰
Formulated in the ratio (unit: parts by weight) shown in Table 4 or Table 5,
In addition, the following various stabilizers are all blended, and mixed for 10 minutes with a small desktop kneader to produce an antistatic resin composition,
Using a desktop press, 145 ° C, 100 kg
f / cm ² , 50 minutes, film thickness 0.8
mm test pieces were prepared. Epoxidized soybean oil 2.0 parts by weight Ba / Zn-based stabilizer 2.5 parts by weight Dibutyltin dilaurate-based stabilizer 0.2 parts by weight

[0071]

[Table 4]

[0072]

[Table 5]

[Examples of Preparation of Comparative Test Pieces 21 to 26] The vinyl chloride-based polymer A and copolymers C ^{1 to} C ² obtained above and polyethylene glycol (M _n = 10000, usually used as an antistatic agent) , PEG) and DOP were blended in the ratio (unit: parts by weight) shown in Table 6, and comparative test pieces 21 to 26 were obtained in the same manner as in Preparation Example 1 of test pieces.

[0074]

[Table 6]

The obtained test pieces 1 to 20 and comparative test piece 21
Physical properties and characteristics of Nos. To 26 were evaluated by the following methods. The results are shown in Tables 7-9.

(1) Haze: Haze was determined in accordance with JIS K6301. (2) Contact angle (unit: degree (°)): The contact angle with water at 20 ° C. was measured by an automatic contact angle measuring device. (3) Concentration rate (unit: times): Specific element / ESCA
The atomic ratio of chlorine was determined and determined. The magnification with respect to the theoretical value when the distribution is assumed to be uniform is shown. Specific element: oxygen (Examples 1, 2, 11, 12, Comparative Example 2)
1-26), nitrogen (Examples 3, 4, 13, 14), phosphorus (Examples 5, 6, 7, 8, 15, 16, 17, 18),
Sulfur (Examples 9, 10, 19, 20).

(4) Surface resistance: surface resistance value (Ω / □)
Is a surface resistance measuring instrument (Yokogawa / Hewlett-Packard Company; product number: 4329A, cell: 16008A)
The measurement was performed on a square plate-shaped test piece formed into a predetermined size under the conditions of a temperature of 20 ° C. and a humidity of 65%.
The method for measuring the surface resistance value was in accordance with JIS K6911. "-" In the table indicates that measurement has not been performed. (5) Bleed-out property: The obtained film was kept at 100 ° C.
After heating for 48 hours, bleed out on the film surface was observed. A case where there was no bleed-out was evaluated as ○, and a case where there was bleed-out was evaluated as x.

[0078]

[Table 7]

[0079]

[Table 8]

[0080]

[Table 9]

[0081]

The antistatic agent comprising the random copolymer of the present invention has a simple production method and has the property of being efficiently concentrated on the surface of the resin composition. It exerts a protective effect Also, the bleed-out resistance is very excellent.

The resin composition containing the antistatic agent is also a composition capable of providing a molded article having excellent antistatic properties.

Claims (9)

[Claims] ( ¹ ) The following polymerized unit (b ¹ ),
² ) and an antistatic agent for a resin comprising a copolymer (B) containing the following polymerized unit (b ³ ). Polymerized unit (b ¹ ): a polymerized unit based on a polymerizable monomer having a hydrophilic or conductive group. Polymerized unit (b ² ): a polymerized unit based on a polymerizable monomer containing a fluorine atom, and a polymerized unit other than the polymerized unit (b ¹ ). Polymerized unit (b ³ ): a polymerized unit based on a polymerizable monomer having compatibility with a resin when a homopolymer is used, and other than the polymerized unit (b ¹ ) and the polymerized unit (b ² ) Polymerized units. 2. The antistatic agent for a resin according to claim 1, wherein the polymerized unit (b ¹ ) is a polymerized unit based on a polymerizable monomer represented by the following formula 1. DQ ¹ -U ¹ Formula 1 wherein the symbols in the formula have the following meanings. D: polymerizable unsaturated group. Q ¹ : a single bond or a divalent linking group. U ¹ : a monovalent group having hydrophilicity or conductivity. 3. The resin antistatic agent according to claim 1, wherein the polymerized unit (b ² ) is a polymerized unit based on a polymerizable monomer represented by the following formula 2. CH ₂ = CR ² COO-Q ² -R ^f Formula 2 where the symbols in the formula have the following meanings. R ² : hydrogen atom or methyl group. Q ² : a single bond or a divalent linking group. R ^f : polyfluoroalkyl group. 4. The polymerized unit (b ³ ) is a polymerized unit based on an alkyl acrylate having 1 to 8 carbon atoms in the alkyl group or a methacrylic acid alkyl ester having 1 to 8 carbon atoms in the alkyl group. Claims 1-3
The antistatic agent for a resin according to any one of the above. 5. The antistatic agent for a resin according to claim 1, wherein the copolymer (B) is a random copolymer. 6. The copolymer (B) has a proportion of the polymerized unit (b ¹ ) of 5 to 90% by weight, a proportion of the polymerized unit (b ² ) of 1 to 57% by weight, and a proportion 4-86 wt% of the unit (b ^3), the resin antistatic agent according to any one of claims 1 to 5. 7. A resin composition comprising the resin antistatic agent according to claim 1 and a resin. 8. The resin composition according to claim 7, wherein the resin is a vinyl chloride resin. 9. A molded article obtained by molding the resin composition according to claim 7 or 8.