JP2000103924A - Additive for resin, resin composition and formed product - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject additive capable of expressing excellent chalking properties without reducing heat stability of a resin by using a specific polymer. SOLUTION: This additive comprises 5-90 wt.% of (A) a polymerization unit of a polymerizable monomer having an organic group expressed by the formula [R1 to R4 are each a 1-18C alkyl; Z is a (substituted) 1-18C alkoxy, a (substituted)alkyl, a (substituted)acyl or H], 1-57 wt.% of (B) a polymerization unit of a polymerizable monomer having fluorine atoms and except the ingredient A, ingredient C and ingredient D, 5-90 wt.% of (C) a polymerization unit of a polymerizable unit having ultraviolet light-absorbing organic group and except the ingredient A and ingredient D, and 4-86 wt.% of (D) a polymerization unit, except the ingredient A, of a polymerizable monomer compatible with a resin when it is made into its homopolymer.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a novel resin additive, particularly a resin additive useful as an additive for a vinyl chloride resin, a resin composition containing the resin additive, and a resin composition containing the resin additive. It relates to a molded article. The molded article obtained by molding the resin composition containing the resin additive of the present invention exhibits excellent performance in weather resistance, particularly in chalking resistance.

[0002]

2. Description of the Related Art A resin composition such as a vinyl chloride resin composition containing a pigment or the like is molded for pipes, rain gutters, deck materials, window frames, and the like, and is widely used outdoors as a colored molded article. ing. However, when a colored molded product is exposed to the outdoors, it not only discolors and fades, but also causes a so-called chalking phenomenon (whitening phenomenon) in which the surface of the portion exposed to sunlight discolors white as if blowing powder. is there.
Further, the choking phenomenon has a problem that the appearance of the molded article is significantly impaired and the mechanical strength is reduced.

[0003]

In order to solve the above problems, a heat stabilizer such as a metallic soap, a lead compound or an organic tin compound, an ultraviolet absorber, an antioxidant,
A molded article of a vinyl chloride resin composition to which a plasticizer, a lubricant, a filler, a coloring agent, or the like has been added, and a vinyl chloride resin composition formed by further adding a copper compound to the resin composition has been proposed. .

[0004] However, the addition of a copper compound has a problem of deteriorating the thermal stability of a vinyl chloride meter resin and a problem of inducing dehydrochlorination of the resin. A method using hydrotalcite in combination (Japanese Patent Application Laid-Open No. Hei 7-118474) has been proposed. However, there was a problem that the molded product obtained by the method had insufficient chalking resistance. A method of adding a compound having a 2,2,6,6-tetramethylpiperidinyl group as a light stabilizer (Japanese Patent Application Laid-Open No. 59-196351) has also been proposed.
The effect is insufficient.

[0005] The present invention provides a resin additive which exhibits excellent choking resistance without deteriorating the thermal stability of the resin, and the appearance and processing in addition to the above-mentioned properties by containing the resin additive. It is intended to provide a resin composition having excellent properties.

[0006]

SUMMARY OF THE INVENTION The present invention has been made to solve the above problems. That is, the present invention
Additive for resin comprising the following polymerized unit (b ¹ ), the following polymerized unit (b ² ), the following polymerized unit (b ³ ), and a copolymer (B) containing the following polymerized unit (b ⁴ ): Provided are a resin composition containing an additive and a resin, and a molded article obtained by molding the resin composition. Polymerized unit (b ¹ ): a polymerized unit of a polymerizable monomer having an organic residue represented by the following formula 1. However, R ¹ to
R ⁴ may be the same or different,
An alkyl group having 1 to 18 carbon atoms, Z is a substituted or unsubstituted alkoxy group having 1 to 18 carbon atoms, a substituted or unsubstituted alkyl group, a substituted or unsubstituted acyl group, or a hydrogen atom.

[0007]

Embedded image

Polymerized unit (b ² ): a polymerized unit of a polymerizable monomer having a fluorine atom, and a polymerized unit (b
¹ ), a polymerized unit (b ³ ), and a polymerized unit other than the polymerized unit (b ⁴ ). Polymerized unit (b ³ ): a polymerized unit of a polymerizable monomer having an ultraviolet-absorbing organic residue, and a polymerized unit other than the polymerized unit (b ¹ ) and the polymerized unit (b ⁴ ). Polymerized unit (b ⁴ ): a polymerized unit of a polymerizable monomer having compatibility with a resin when formed into a homopolymer, and a polymerized unit other than the polymerized unit (b ¹ ).

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION The polymer unit (b ¹ ) is a polymer unit of a polymerizable monomer having an organic residue represented by the formula 1 [hereinafter referred to as a specific polymerizable monomer]. R ^{1 to} R in Formula 1
⁴ is preferably an alkyl group having 1 to 6 carbon atoms,
Particularly, a methyl group, an ethyl group, or a propyl group is preferable.

Z is preferably a substituted or unsubstituted alkyl group having 1 to 18 carbon atoms or a substituted or unsubstituted alkoxy group, particularly a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms, or a substituted or unsubstituted alkyl group. A substituted alkoxy group having 1 to 6 carbon atoms is preferred. When substituted, examples of the substituent include a hydroxyl group, an epoxy group, an acyloxy group, and a hydroxyallyl group.

Specific examples of Z include methyl, ethyl, propyl, butyl, hexyl, octyl,
Methoxy, ethoxy, propoxy, butoxy,
Examples include a dodecyl group, a 2-hydroxyethyl group, a 2-hydroxypropyl group, a 2-hydroxybutyl group, a 2-epoxypropyl group, and an acetoxyethyl group. Specific examples of the organic residue represented by Formula 1 include the groups in the following specific examples.

The specific polymerizable monomer is preferably a polymerizable monomer in which a polymerizable group is bonded to a known compound that can be used as a light stabilizer, and an acryloyl group is added to the organic residue represented by the formula (1). , A polymerizable monomer to which a polymerizable group such as a methacryloyl group, an allyl group, or a vinyl group is bonded, and a polymerizable monomer represented by the following formula 2 is particularly preferable. In the following, an acryloyl group and a methacryloyl group are collectively referred to as a (meth) acryloyl group, and an acrylate or methacrylate is referred to as a (meth) acrylate. CH ₂ = CR ⁵ COO-U ¹ Formula 2 where R ⁵ represents a hydrogen atom or a methyl group, and U ¹ represents an organic residue represented by Formula 1. Further, as Formula 2, a compound in which a (meth) acryloyl group is bonded to N-methyl-2,2,6,6-tetramethylpiperidine is preferable. Two or more kinds of polymerized units (b ¹ ) may be present in the copolymer (B).

Specific examples of the polymerizable monomer represented by the formula 2 include the following groups.

N-methyl-2,2,6,6-tetramethyl-4- (meth) acryloyloxypiperidine,
Acetoxy-2,2,6,6-tetramethyl-4- (meth) acryloyloxypiperidine, N-methoxy-
2,2,6,6-tetramethyl-4- (meth) acryloyloxypiperidine, N-ethoxy-2,2,6,6
-Tetramethyl-4- (meth) acryloyloxypiperidine, N-butoxy-2,2,6,6-tetramethyl-4- (meth) acryloyloxypiperidine.

Further, specific polymerizable monomers other than the polymerizable monomer represented by the formula 2 include N- (N-methyl-2,
2,6,6-tetramethyl-4-piperidine) maleimide, N- (N-methoxy-2,2,6,6-tetramethyl-4-piperidine) maleimide and the like.

The polymer unit (b ² ) is a polymer unit of a polymerizable monomer having a fluorine atom. The polymerized unit (b ² ) is
Since it has a fluorine atom, it is considered to have a function of transferring the copolymer (B) to the surface in the resin composition. As the polymerizable monomer having a fluorine atom, a fluorine-containing olefin such as vinyl fluoride or a compound having both a polymerizable group and a fluorine atom-containing group in the molecule is preferable.
As the fluorine atom-containing group, a polyfluoroalkyl group is preferable.

In the following, the polyfluoroalkyl group is referred to as an ^Rf group. The polymerizable monomer having a fluorine atom, a polymerizable monomer having R ^f group is preferably, for example, having ^the R ^f group (meth) acrylate, vinyl compounds having ^the R ^f group, an allyl having ^the R ^f group And the like.

The R ^f group is a group in which two or more hydrogen atoms of an alkyl group have been replaced by 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)] × 60 (%) when expressed by 100 (%)
The above is preferable, and particularly preferable is 80% or more. Also, R
^{The f} group may be a group in which an etheric oxygen atom (—O—) is inserted between carbon-carbon single bonds, and specific examples thereof include oxypolyfluoroethylene and oxypolyfluoropropylene. An R ^f group having an ^{oxypolyfluoroalkylene} moiety is exemplified.

The ^Rf group preferably has 1 to 20 carbon atoms,
To 16 are more preferable, and 6 to 12 are particularly preferable. 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 -, 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 R ^F group may have an etheric oxygen atom (—O—) inserted between carbon-carbon bonds in the R ^F group.
The R ^F group preferably has 1 to 20 carbon atoms, and particularly preferably 4 to 16 carbon atoms. Also, R ^F group is linear or branched structure R ^F
A linear R ^F group represented by F (CF ₂ ) _n- [n is an integer of 4 to 16], and n of the group is 6 to 12
Is particularly preferred.

R^f The following structures are specific examples of the group.
But not limited to these. In the following example,
Are groups having the same molecular formula but different structures.
"Isomeric groups" are also included. C_Two F_Five -, C_Three F₇ − [F
(CF_Two )_Three −, And (CF_Three )_Two CF-
No. ], C_Four F₉ − [F (CF_Two )_Four −, (CF_Three )_Two 
CFCF_Two −, (CF_Three )_Three C-, CF_Three CF_Two CF
(CF_Three )-], C_Five F₁₁− [F (CF_Two )_Five 
−, (CF_Three )_Two CF (CF_Two )_Two −, (CF_Three )_Three C
CF_Two -, CF _Three CF_Two CF (CF_Three ) CF_Two -Such as
Containing structurally isomeric groups], C₆ F₁₃− [F (CF_Two )_Three C
(CF_Three )_Two -, Etc.], C₈ F₁₇
-, C_TenF_{twenty one}-, C₁₂F_{twenty five}-, C_FifteenF₃₁-, HC_t F_2t
− (T is an integer of 1 to 18), (CF_Three )_Two CFC_s F_2s
-(S is an integer of 1 to 15) and the like.

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- (however, 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.

As the polymerizable monomer having a fluorine atom, a (meth) acrylate having an R ^f group represented by the following formula 3 is preferable. CH ₂ ＣＲCR ⁶ COO—Q—R ^f Formula 3 wherein R ⁶ represents a hydrogen atom or a methyl group, Q represents a divalent organic linking group or a single bond, and R ^{f
Represents an} R ^f group. Q is preferably a divalent organic linking group, particularly preferably those listed in the specific examples described below.

Examples of the (meth) acrylate having an R ^f group as a polymerizable monomer having a fluorine atom include the following compounds. However, the symbols R ⁶ and R ^f in the compound have the same meaning as in Formula 3.

[0025]

Embedded image ^{_{CH 2 = CR 6 COOCH 2 CH}} 2 R f, CH 2 = CR 6 COOCH 2 CH 2 N (CH 2 CH 2 C
^{_{H 3) COR f, CH 2}} = CR 6 COOCH (CH 3) CH 2 R f, CH 2 = CR 6 COOCH 2 CH 2 N (CH 3) SO 2
R ^f , CH ₂ = CR ⁶ COOCH ₂ CH ₂ N (CH ₃ ) COR
^{_{f, CH 2 = CR 6 COOCH}} 2 CH 2 N (CH 2 CH 3)
SO ₂ R ^f , CH ₂ = CR ⁶ COOCH ₂ CH ₂ N (CH ₂ CH ₃ )
^{_{COR f, CH 2 = CR 6}} COOCH 2 CH 2 N (CH 2 CH 2 C
H ₃ ) SO ₂ R ^f , CH ₂ ＣＲCR ⁶ COOCH (CH ₂ Cl) CH ₂ OCH
_{2 CH 2 --N (CH 3)} SO 2 R f.

One or more polymerized units (b ² ) may be present in the copolymer (B). When two or more types of polymerized units (b ² ) are present, the number of types of polymerized units of the polymerizable monomer having an R ^f group having a different structure is two or more, or the number of carbon atoms of the R ^f group is different. It is preferred that the polymerizable monomer having an R ^f group has two or more polymer units.

The polymerizable monomer having an R ^f group is represented by the formula 3
Compounds in which ^f is a perfluoroalkyl group having 4 to 16 carbon atoms are preferred. When the number of carbon atoms in ^Rf is small, the surface migration in the resin may be insufficient. On the other hand, ^if the number of carbon atoms in R ^f is too large, the compatibility of the compound represented by Formula 3 with other polymerizable monomers may decrease, and the yield during copolymerization may decrease. Further, the compatibility with the resin may be reduced, and the surface transferability may be reduced.

The polymerized unit (b ³ ) is a polymerized unit of a polymerizable monomer having an ultraviolet absorbing organic residue [hereinafter referred to as a UV absorbing polymerizable monomer]. As the ultraviolet-absorbing organic residue, a residue having an ultraviolet-absorbing action of various organic compounds known as an ultraviolet absorber is suitable, and a group having a benzophenone skeleton, a group having a benzotriazole skeleton, a cyanoacrylate skeleton And a group containing a salicylic acid skeleton.

Specific examples of the UV-absorbing polymerizable monomer include:
A polymerizable monomer in which a polymerizable group such as a (meth) acryloyl group or a vinyl group is bonded to a known UV-absorbing compound such as a benzophenone-based compound or a benzotriazole-based compound as a UV-absorbing agent is preferable. A (meth) acrylate having an ultraviolet absorbing organic residue represented by the following formula 4 in which a (meth) acryloyl group is bonded to a compound is preferable. CH ₂ = CR ⁷ COO-U ² Formula 4 In Formula 4, R ⁷ represents a hydrogen atom or a methyl group, and U ² represents an ultraviolet absorbing organic residue.

Specific examples of the compound represented by Formula 4 include:
As the ultraviolet absorbing residue, a compound having a benzophenone compound residue or a benzotriazole compound residue is preferable. The polymerized unit (b) in the copolymer (B)
³ ) may be present in two or more types.

Specific examples of the compound represented by the formula 4 having a residue of a benzophenone compound include the following compounds. 2-hydroxy-4- (meth) acryloyloxybenzophenone, 2-hydroxy-4- (2-
(Meth) acryloyloxyethoxy) benzophenone, 2-hydroxy-4- (2-acryloyloxypropoxy) benzophenone, 2,2′-dihydroxy-
4- (meth) acryloyloxybenzophenone, 2,
2'-dihydroxy-4- (2- (meth) acryloyloxyethoxy) benzophenone, 2-hydroxy-4
-(Meth) acryloyloxy-2'-hydroxypropylbenzophenone.

Specific examples of the compound represented by the formula 4 having a residue of a benzotriazole compound include the following compounds. 2- {2-hydroxy-5-((meth) acryloyloxy) phenyl} benzotriazole, 2- {2-hydroxy-3-methyl-5-((meth) acryloyloxy) phenyl} benzotriazole, 2- {2 -Hydroxy-3-t-butyl-5-
((Meth) acryloyloxy) phenyl} benzotriazole, 2- {2-hydroxy-5- (2- (meth)
(Acryloyloxyethyl) phenyl} benzotriazole, 2- {2-hydroxy-5- (3- (meth) acryloyloxypropyl) phenyl} benzotriazole, 2- {2-hydroxy-3-t-butyl-5- (2
-(Meth) acryloyloxyethyl) phenyl dibenzotriazole.

2- {2-hydroxy-3-t-butyl-
5- (3- (meth) acryloyloxypropyl) phenyl} benzotriazole, 2- {2-hydroxy-3
-Methyl-5- (2- (meth) acryloyloxyethyl) phenyl} benzotriazole, 2- {2-hydroxy-3-methyl-5- (3- (meth) acryloyloxypropyl) phenyl} benzotriazole, 2-
{2-Hydroxy-5- (2- (meth) acryloyloxyethyl) phenyl} -5-chlorobenzotriazole, 2- {2-hydroxy-5- (2- (meth) acryloyloxyethyl) phenyl} -5- Methylbenzotriazole, 2- {2-hydroxy-5- (2- (2-
(Meth) acryloyloxyethoxycarbonyl) ethyl) phenyl} benzotriazole, 2- {2-hydroxy-5- (2- (meth) acryloyloxyethoxy) phenyl} benzotriazole, 2- {2-hydroxy-5- (2 -(Meth) acryloyloxypropoxy) phenyl} benzotriazole.

Specific examples of the compound represented by the formula 4 other than the above include (2-cyano-2-ethyl-3,3-
Diphenyl-hexyl) (meth) acrylate and the like.

The polymerized unit (b ⁴ ) is a polymerized unit of a polymerizable monomer (hereinafter, referred to as a compatible monomer) having compatibility with a resin when formed into a homopolymer. The compatible monomer is
It is considered to have a function as an anchor for the resin. Two or more types of the polymerized unit (b ⁴ ) in the copolymer (B) may be present.

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. Furthermore, compatibility monomers, S _p values in the case of a homopolymer, is preferably in the range of about 7.5 to 11.5 as an absolute value, in particular 8.
It is preferably from 5 to 10.5.

As the compatible monomer, for example, (meth)
Acrylic ester-based polymerizable monomers, vinyl ester-based polymerizable monomers, vinyl cyanide-based polymerizable monomers, aromatic vinyl-based polymerizable monomers, or combinations thereof, and particularly (meth) A polymerizable monomer having an acryloyl group is preferred.

When the compatible monomer is a polymerizable monomer having a (meth) acryloyl group, alkyl (meth)
Acrylic acid rates are preferred. The alkyl (meth) acrylate preferably has 1 to 8 carbon atoms in the alkyl group portion, more preferably 1 to 6 carbon atoms, particularly methyl (meth) acrylate [ _Sp value of homopolymer = 9.
5], ethyl (meth) acrylate, butyl (meth) S _p value of acrylate [homopolymer = 8.6] and the like are preferable.

When the compatible monomer is a vinyl ester polymerizable monomer, examples thereof include vinyl acetate, vinyl propionate, and vinyl butyrate. Examples of the vinyl cyanide polymerizable monomer include acrylonitrile, methacrylonitrile, and the like. Examples of the aromatic vinyl polymerizable monomer include α-methylstyrene, vinyltoluene,
Chlorostyrene and the like.

The copolymer (B) of the present invention may contain polymerized units other than the above-mentioned polymerized units (b ¹ ) to (b ⁴ ) (hereinafter, referred to as other polymerized units). The other polymerization units are polymerization units of a polymerizable monomer other than the polymerization units (b ¹ ) to (b ⁴ ) (hereinafter, referred to as other polymerizable monomers). Further, among those described as compatible monomers, polymerized units that are not compatible with the resin to which the resin additive of the present invention is added may be used.

Other polymerizable 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 in the alkyl group. preferable. When polymerized units of other polymerizable monomers are included, the content is preferably 30% by weight or less in the copolymer (B), particularly preferably more than 0% by weight to 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 ⁴ ). The chain structure of the copolymer (B) may be any of graft, block and random, and a random copolymer is preferred.

The ratio of the polymerized unit (b ¹ ) and the ratio of the polymerized unit (b ³ ) in the copolymer (B) is preferably 5 to 90% by weight in the copolymer. The ratio is 9
If it exceeds 0% by weight, the ratio of the polymerized unit (b ² ) and the polymerized unit (b ⁴ ) becomes relatively small, and the surface transferability of the resin additive may be reduced. If the proportion is less than 5% by weight, the resolution of the hydroperoxide on the resin surface and the ultraviolet absorbing ability may be insufficient, or the properties of the resin may be deteriorated due to the increased amount of the resin additive. .

Further, the polymerized unit (b ¹ ) and the polymerized unit (b
³ ratio) of (weight ratio), polymerized units (b ¹⁾ / polymerized units (b ³⁾ (weight ratio) is preferably 3/7 to 7/3. If the ratio is less than 3/7, the ultraviolet-absorbing organic residues in the polymerized unit (b ³ ) are oxidized to lower the ultraviolet-absorbing ability, and the oxidized ultraviolet-absorbing residues work as a photosensitizer. The deterioration of the resin surface may be promoted. On the other hand, when the ratio is more than 7/3, the ultraviolet absorbing ability on the resin surface is reduced, and the anti-chalking ability may be insufficiently expressed.

The proportion of the polymerized unit (b ² ) is preferably 1 to 57% by weight in the copolymer (B), and particularly preferably 3 to 57% by weight.
Preferably it is ~ 38% by weight. When the proportion is less than 1% by weight, the fluorine content in the copolymer (B) decreases,
The surface transferability derived from fluorine atoms is not exhibited, and the concentration of the copolymer (B) in the vicinity of the resin surface may be insufficient. On the other hand, if the proportion exceeds 57% by weight, the compatibility of the copolymer (B) with the resin (A) becomes too high, and the surface transferability decreases. The concentration of B) may decrease. Polymerized unit (b
The proportion of ⁴ ) is preferably from 4 to 86% by weight, particularly preferably from 24 to 67% by weight, in the copolymer (B).

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 above polymerizable monomer and, if necessary, another polymerizable monomer are combined with azobisisobutyronitrile (hereinafter referred to as AI).
BN) or a radical initiator such as benzoyl peroxide, for example, a method of suspension polymerization, emulsion polymerization, or solution polymerization. Examples of the solution used for the solution polymerization include toluene, tetrahydrofuran (hereinafter referred to as THF),
Acetone, 1,1,2-trichlorotrifluoroethane and the like can be mentioned.

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 (A) may be insufficient, and if _Mn is more than 30,000, the mobility of the molecules may be low and the concentration rate on the surface may be insufficient. The glass transition temperature T _g of the copolymer (B) is preferably 80 ° C. or less, S _p value 6-8 is preferred. The resin additive of the present invention comprising the copolymer (B) can be added to the resin (A) and used as a resin composition. As the resin (A), a resin compatible with the resin additive of the present invention is employed, and various known resins can be used.

As the resin (A), vinyl chloride resin,
Polyester resin such as polyethylene terephthalate, polybutylene terephthalate, nylon 11, nylon 1
2, polyamide resins such as nylon 66 and nylon 6, acrylic resins such as polymethyl methacrylate, polystyrene resins, polycarbonate resins, polyurethane resins, and copolymers of acrylonitrile, styrene and butadiene (ABS resins), and the like. Vinyl chloride resins are preferred. That is, the resin additive of the present invention is preferably used as an additive for a vinyl chloride resin. The amount of the resin additive is preferably 0.5 to 20% by weight based on the resin (A). If the amount is less than 0.5% by weight, desired surface properties may not be obtained. If the amount exceeds 20% by weight, physical properties of the resin (A) may be reduced.

When a vinyl chloride resin is used as the resin (A), the vinyl chloride resin may be a homopolymer of vinyl chloride, a vinyl chloride-vinyl acetate copolymer, or a vinyl chloride-acrylate copolymer. And a vinyl chloride-vinylidene chloride copolymer, and a homopolymer of vinyl chloride is preferred. The vinyl chloride resin may be one kind or a mixture of two or more kinds.

The vinyl chloride resin is preferably a vinyl chloride resin obtained by a known production method, that is, a suspension polymerization method, an emulsion polymerization method, or a bulk polymerization method. Further, the vinyl chloride resin may be a soft vinyl chloride resin to which a plasticizer is added. The average degree of polymerization of the vinyl chloride resin is preferably from 400 to 1500, and
Is particularly preferred. If the average degree of polymerization is too small, the weather resistance of the resin itself is reduced, and mechanical properties such as impact resistance and elastic modulus, and thermal stability are sometimes reduced. If the average degree of polymerization is too large, the moldability may decrease, which is not preferable.

The resin composition of the present invention may contain other components (hereinafter, referred to as other compounding agents) together with the resin additive and the resin (A). Other compounding agents include stabilizers for resins, impact modifiers, lubricants, pigments, antistatic agents, antioxidants, fillers, foaming agents, flame retardants, and the like. When another compounding agent is added, the amount of the compounding agent is preferably set to 0.05 to 20% by weight in the resin composition.

Representative examples of other compounding agents include organic tin heat stabilizers such as dibutyltin dilaurate and dibutyltin malate, and aliphatic carboxylic acids or aliphatic carboxylate salts such as stearic acid, calcium stearate, and zinc stearate. , Inorganic stabilizers, epoxy compounds such as epoxidized soybean oil, stabilizers such as organic phosphates, methyl methacrylate-
Butadiene-styrene copolymer (MBS), impact modifiers such as acrylic silicone, lubricants such as higher fatty acids,
Fillers such as phenolic antioxidants, carbon black, silica, calcium carbonate and the like are included.

The resin composition can be processed into various forms by a molding method according to the purpose. As the molding method, injection molding, extrusion molding, which is generally applied to thermoplastic resins,
A method such as press molding or calender molding is used. Further, in the present invention, after the resin composition is molded, the resin (A) is heated at a temperature near T _g (glass transition temperature) for several hours, so that the resin additive on the surface of the molded body can be efficiently used. Can be concentrated. Examples of the molded article obtained by molding the resin composition of the present invention include pipes, joints, flat and corrugated sheets for building materials,
Rain gutters, deck materials, window frames, and the like. The molded article of the present invention is provided with excellent water repellency, weather resistance, and chalking resistance on the surface without deteriorating the physical properties of the resin.

[0054]

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) Method of Measuring Number Average Molecular Weight and Molecular Weight Distribution The number average molecular weight M _n and molecular weight distribution M _w / M _n were measured by gel permeation chromatography [HLC80 manufactured by Tosoh Corporation].
20] under the following conditions. Column: TSK gel column manufactured by Tosoh Corp. Detector: 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. Tetramethylsilane was used as a reference material. (3) Melt Viscosity The glass transition temperature T _g (° C.) was measured using DSC3200 (manufactured by Mac Science).

[Synthesis Example of Resin (A)] 3 g of partially saponified polyvinyl alcohol (trade name: Gohsenol KH-20, manufactured by Nippon Synthetic Chemical Co., Ltd.), 0.174 g of AIBN, and 1170 g of ion-exchanged water were placed in a pressurized reactor. In addition, after purging with nitrogen gas, 300 g of vinyl chloride was charged. 65 ° C
After reacting for 6 hours, unreacted vinyl chloride was 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 800. Hereinafter, this polymer is referred to as polymer A.
S _p value of the polymer A is 9.5.

[0058] inside the synthesized Synthesis Example 1 Copolymer B ¹ glass flask 1 liter with nitrogen,
Perfluoroalkyl ethyl acrylate having an average number of carbon atoms of 9 perfluoroalkyl group [CH ₂ ＣＨCHCO
OCH ₂ CH ₂ R ^F, hereinafter referred to as FA] 100 g, methyl methacrylate (hereinafter, referred to as MMA. Alone S _p value of the polymer ^{9.5 (cal / cm 3) 1/2} .200g,
2-hydroxy-4-methacryloyloxy-2′-hydroxypropylbenzophenone (manufactured by Otsuka Chemical) (UV
A) 150 g, 150 g of N-methyl-2,2,6,6-tetramethyl-4-methacryloyloxypiperidine (manufactured by Asahi Denka, referred to as HALS), 5.0 g of AIBN, and 2500 g of toluene were charged and reacted at 60 ° C. for 8 hours. I let it.

After cooling the flask, the content was poured into methanol to obtain a copolymer. _Mn of the obtained copolymer was 12000, and _Mw / _Mn was 1.86. ¹ H-N
As a result of determining the composition ratio of the copolymer from MR, FA / MMA
/ UVA / HALS = 98/205/142/158
(Weight ratio). Hereinafter, this copolymer is referred to as polymer B ¹
That.

[Synthesis Examples 2 to 6 and Comparative Synthesis Examples 1 and 2] Synthesis of Copolymers B ^{2 to} B ⁹ and Comparative Copolymers C ^{1 to} C ² Preparation Compositions (Amount, Unit) shown in Tables 1 and 2 : G), a polymerizable monomer, a polymerization initiator, and 2,500 g of toluene were charged, and copolymers B ^{2 to} B ⁹ and comparative copolymers C ^{1 to} C ² were synthesized under the same conditions as in Synthesis Example 1. M of the obtained copolymer
_n , composition ratio (unit: weight ratio) and glass transition temperature are shown in Table 1.
It is shown in Table 2.

However, in Tables 1 and 2, butyl acrylate is abbreviated as BA, and N-methoxy-2,2,6,6-tetramethyl-4-methacryloyloxy-piperidine is abbreviated as NO-HALS. NO-HALS is Reference Example 1.
The one synthesized by the method shown in FIG.

REFERENCE EXAMPLE 1 100 g of 4-hydroxy-2,2,6,6-tetramethylpiperidine, 47 g of acetylhydroperoxide and 500 g of water were added to a 1 L glass flask whose inside was replaced with nitrogen. Stirring was performed for 4 hours. The precipitate formed by cooling the flask to room temperature was filtered, collected, dried, and then recrystallized in toluene to obtain 2,2.
108 g of 2,6,6-tetramethyl-4-hydroxypiperidine-N-oxide were obtained. In a separate 1 L glass flask, 100 g of 2,2,6,6-tetramethyl-4-hydroxypiperidine-N-oxide, methyl iodide 8
After adding 1 g and 500 g of toluene and reacting at 50 ° C. for 4 hours, the precipitate obtained by cooling the flask was recovered, dried, and recrystallized in toluene to obtain N-methoxy-2,2,2.
6,6-tetramethyl-4-hydroxy-piperidine 1
10 g were obtained. In another 1 L glass flask, add N
-Methoxy-2,2,6,6-tetramethyl-4-hydroxypiperidine (100 g), hydroquinone (3 g), triethylamine (50 g) and toluene (500 g) were added, and methacryloyloxychloride (53 g) was added dropwise under ice cooling over about 1 hour. The reaction was performed at a temperature of 5 ° C. for 5 hours. After cooling the flask, the solvent was removed under reduced pressure, and the obtained solid was recrystallized in toluene to give N-methoxy-2,2,6,6-
Tetramethyl-4-methacryloyloxypiperidine 1
45 g were obtained.

[0063]

[Table 1]

[0064]

[Table 2]

[Examples of Preparation of Test Specimens 1-36] 100 parts by weight of polymer A obtained above, polymers B ^{1 and} B ² , dibutyltin malate (trade name: TN1000, manufactured by Sakai Chemical Co., Ltd.)
3 parts by weight of stearic acid (hereinafter referred to as S)
0.5 parts by weight of tA), titanium oxide, and carbon black (hereinafter, referred to as CB) were blended in proportions (unit: parts by weight) shown in Tables 3 to 5, respectively, and 180 parts by a biaxial roll.
After kneading at 180 ° C., press molding was performed at 180 ° C. and 200 kg / cm ² to obtain test pieces 1 to 36 of a resin composition having a thickness of 3 mm.

[0066]

[Table 3]

[0067]

[Table 4]

[0068]

[Table 5]

[Examples of Preparation of Comparative Test Pieces 37 to 44] Polymer A, polymer C ¹ , polymer C ² , and an ultraviolet absorbent (trade name: Tinuvin P, manufactured by Ciba Geigy, hereinafter referred to as TP)
), A light stabilizer (trade name: Tinuvin 123, manufactured by Ciba-Geigy), copper acetate, TN, S
tA, titanium oxide, and CB were blended at the ratio (unit: parts by weight) shown in Table 6, and comparative test pieces 37 to 44 were obtained in the same manner as in the preparation example 1 of the test piece.

[0070]

[Table 6]

The obtained test pieces 1 to 36 and comparative test piece 37
Physical properties and characteristics of Nos. To 44 were evaluated by the following methods. The results are shown in Tables 7 to 10. In addition, "-" in a table | surface shows that it has not evaluated. (1) Melt viscosity (unit: 10 ⁴ poise): temperature 180 ° C., nozzle diameter 1 mm, L / D = 1 according to Capillograph
0 and a shear rate of 121.6 sec ^-1 . (2) Thermal stability: A test piece was used as a gear oven (Toyo Seiki)
Was measured at 190 ° C. for 40 minutes to measure the time (HS) until blackening, and evaluated according to the following criteria. ：: HS is 40 minutes or more, Δ: HS is 30 minutes or more and less than 40 minutes, ×: HS is less than 30 minutes.

(3) Water repellency (unit: degree (°)): The contact angle with water at 20 ° C. was measured by an automatic contact angle measuring device. (4) Concentration ratio (unit: times): The atomic ratio of fluorine / chlorine was determined by ESCA and determined. The magnification to the theoretical value in the case of uniform distribution is shown.

(5) Weather resistance: Performed according to the method of JIS-A1415. The test specimen was measured for 250 hours (W250) by a WS-type accelerated exposure test sunshine weatherometer.
1000 hours (W1000), 2000 hours (W200
0) Accelerated exposure. Coloring and chalking were evaluated according to the following criteria. D: ΔE is less than 3 (ΔE indicates the degree of whitening) D: ΔE is 3 or more and less than 6, D: ΔE is 6 or more and less than 9, D ×: ΔE is 9 or more, D: Surface ○: Chalking was observed in less than half of the surface area, △: Chalking was observed in more than half of the surface area, ××: Chalking was observed on the entire surface. .

[0074]

[Table 7]

[0075]

[Table 8]

[0076]

[Table 9]

[0077]

[Table 10]

[0078]

The additive for a resin of the present invention has a simple manufacturing method, and exhibits excellent anti-chalking properties on the surface of a molded product when added to a resin and molded. In addition, the resin additive of the present invention does not decrease the thermal stability of the resin itself, and is excellent in ultraviolet absorbing action and water repellency. That is, the resin additive of the present invention is a practically excellent additive in economical efficiency and physical properties. A molded article obtained by molding the resin composition containing the resin additive of the present invention has excellent weather resistance, and exhibits excellent anti-coloring performance and chalking performance. Further, since the resin additive of the present invention is also excellent in heat resistance, the conventional molding method, that is, injection molding,
Extrusion molding and the like can be adopted, and the moldability and workability are also excellent. Further, the molded article of the present invention is excellent in appearance and workability.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification code FI Theme coat (Reference) C08L 33:16) F-term (Reference) 4J002 BC031 BD031 BD041 BD051 BD081 BD091 BD101 BG061 BG072 BG082 BN151 CF061 CF071 CG001 CK021 CL011 CL021 CL031 FD010 FD030 FD052 GL00

Claims (10)

[Claims] ( ¹ ) The following polymerized unit (b ¹ ),
² ), the following polymerized unit (b ³ ), and the following polymerized unit (b
⁴ ) An additive for a resin comprising a copolymer (B) containing: Polymerized unit (b ¹ ): a polymerized unit of a polymerizable monomer having an organic residue represented by the following formula 1. However, R ¹ to
R ⁴ may be the same or different,
An alkyl group having 1 to 18 carbon atoms, Z is a substituted or unsubstituted alkoxy group having 1 to 18 carbon atoms, a substituted or unsubstituted alkyl group, a substituted or unsubstituted acyl group, or a hydrogen atom. Embedded image Polymerized unit (b ² ): a polymerized unit of a polymerizable monomer having a fluorine atom, and a polymerized unit other than the polymerized unit (b ¹ ), the polymerized unit (b ³ ), and the polymerized unit (b ⁴ ). Polymerized unit (b ³ ): a polymerized unit of a polymerizable monomer having an ultraviolet-absorbing organic residue, and a polymerized unit other than the polymerized unit (b ¹ ) and the polymerized unit (b ⁴ ). Polymerized unit (b ⁴ ): a polymerized unit of a polymerizable monomer having compatibility with a resin when formed into a homopolymer, and a polymerized unit other than the polymerized unit (b ¹ ). 2. The resin additive according to claim 1, wherein the polymer unit (b ¹ ) is a polymer unit of a polymerizable monomer represented by the following formula 2. CH ₂ = CR ⁵ COO-U ¹ Formula 2 where the symbols in the formula have the following meanings. R ⁵ : a hydrogen atom or a methyl group. U: Organic residue represented by the following formula 1. However, R ^{1 to} R ⁴ in the formula 1 may be the same or different and each is an alkyl group having 1 to 18 carbon atoms, and Z is a substituted or unsubstituted alkoxy group having 1 to 18 carbon atoms. A group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted acyl group, or a hydrogen atom. Embedded image 3. The resin additive according to claim 1, wherein the polymer unit (b ² ) is a polymer unit of a polymerizable monomer represented by the following formula 3. CH ₂ = CR ⁶ COO-Q-R ^f Formula 3 where the symbols in the formula have the following meanings. R ⁶ : a hydrogen atom or a methyl group. Q: divalent organic linking group or single bond. R ^f : polyfluoroalkyl group. 4. The resin additive according to claim 1, wherein the polymer unit (b ³ ) is a polymer unit of a polymerizable monomer represented by the following formula 4. CH ₂ = CR ⁷ COO-U ² Formula 4 where the symbols in the formula have the following meanings. R ⁷ : a hydrogen atom or a methyl group. U ² : UV absorbing organic residue. 5. An alkyl acrylate wherein the polymerized unit (b ⁴ ) has 1 to 8 carbon atoms in the alkyl group and / or an alkyl methacrylate wherein the alkyl group has 1 to 8 carbon atoms. The resin additive according to any one of claims 1 to 4, which is a polymerized unit of 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, b ³ ) is 5 to 5.
90% by weight, and the ratio of the polymerized unit (b ⁴ ) is 4%.
The resin additive according to any one of claims 1 to 5, wherein the amount is from -86% by weight. 7. A resin composition containing the resin additive according to claim 1 and a resin (A). 8. The resin composition according to claim 7, wherein the resin (A) is a vinyl chloride resin. 9. The resin composition according to claim 1, wherein said resin additive is 0.05% by weight.
The resin composition according to claim 7, wherein the content of the resin composition is about 20% by weight. 10. A molded article obtained by molding the resin composition according to claim 7, 8, or 9.