JP2002338778A - Graft copolymer composition, thermoplastic resin composition containing the same, and molded item thereof - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a graft copolymer composition excellent in interaction with a fatty acid amide; a thermoplastic resin composition which is inhibited from bleeding, thus keeping a good external appearance, and is excellent in moldability and resistances to scratch, abrasion, and flexing; and a molded item thereof. SOLUTION: The graft copolymer composition comprises 50-99 wt.% graft copolymer and 1-50 wt.% fatty acid amide prepared from a 10-25C fatty acid. The graft copolymer comprises olefin polymer segments (a) as the trunk component and vinyl polymer segments (b) formed from a vinyl monomer as the branch component and has a multiphase structure wherein either the trunk component or the branch component forms a disperse phase comprising particles having particle sizes of 0.001-10 μm in the other component. The thermoplastic resin composition comprises 1-50 wt.% graft copolymer composition and 50-99 wt.% thermoplastic olefin resin. The molded item is obtained by molding the thermoplastic resin composition.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a graft copolymer composition having excellent interaction with a fatty acid amide, capable of suppressing bleeding and maintaining its appearance, and having good scratch resistance and abrasion resistance over a long period of time. The present invention relates to a thermoplastic resin composition having excellent bending resistance and moldability, and a molded article thereof.

[0002]

2. Description of the Related Art Among thermoplastic resins, in particular, olefin-based thermoplastic resins are widely used in recent years because they are lightweight, easy to recycle, have high cost performance, and do not generate toxic gas when burned. Have been.

[0003]

However, a molded article obtained by molding polypropylene, polyethylene or an olefinic thermoplastic elastomer as an olefinic thermoplastic resin has a smaller size than a molded article made from a vinyl chloride resin. However, there is a defect that the scratch resistance and abrasion resistance are inferior, and improvement thereof is strongly desired.

For example, olefin-based thermoplastic elastomers used in automobile parts, such as moldings and glass run channels, which have a sealing function in contact with door glass, generally have a resistance so that the glass can be raised and lowered smoothly. In order to reduce the size and reduce the wear, a nylon film or the like is used by being bonded to its surface with an adhesive. However, the adhesive strength between the olefin-based thermoplastic elastomer and the nylon film cannot be said to be sufficient, and in particular, in an environment such as a high-temperature and high-humidity atmosphere or a solvent spray, the defect that the peeling easily occurs between the base layer and the skin. was there.

In JP-A-2000-327848, a door glass weather strip having abrasion resistance is obtained by adding a fine powder and an alkyl-modified organosiloxane to an olefin-based thermoplastic elastomer. Therefore, there is no need to attach films, and the problem of peeling has been solved. However, in order to obtain a practical effect, a large amount of these additives is required, and since the compatibility between the olefin-based thermoplastic elastomer of the base material and these additives is low, the molded member is bent. In this case, there is a problem that whitening occurs and the bending resistance is low.

JP-A-2000-26668 proposes a glass run channel obtained by adding an organosiloxane and a higher fatty acid amide to an olefin-based thermoplastic elastomer. However, the higher fatty acid amide vaporized particularly in a high-temperature and high-humidity atmosphere, and the glass and the like were easily clouded, and the appearance was likely to be poor.
This is to maintain the slidability of the members for a long time.
This is because the higher fatty acid amide was excessively present on the surface of the member and was in a state of being easily vaporized.

On the other hand, as for the polypropylene resin, Japanese Patent Application Laid-Open No. Hei 10-53673 proposes a polypropylene resin composition excellent in abrasion resistance obtained by adding a specific nucleating agent and a lubricant to the polypropylene resin. However, due to the crystallinity of polypropylene, there is a problem that the effect of the lubricant does not last for a long time.

Further, in recent years, in addition to the complicated shape of the molded article of the olefinic thermoplastic resin, shortening of the molding cycle is required from the viewpoint of cost, and the loss of molding pressure is reduced. There is a demand for a material having good flowability and excellent moldability, which can be obtained.

The present invention has been made by focusing on the problems existing in the prior art as described above. The aim is to maintain a good appearance by suppressing the bleeding, a graft copolymer composition having excellent interaction with fatty acid amide, good scratch resistance and abrasion resistance, and bending resistance and An object of the present invention is to provide a thermoplastic resin composition having excellent moldability and a molded article thereof.

[0010]

In order to achieve the above-mentioned object, a graft copolymer composition according to the first invention comprises an olefin polymer segment (a) as a main component and at least one vinyl-based polymer segment. A multiphase in which a vinyl polymer segment (b) formed from a monomer is used as a branch component and one segment forms a dispersed phase as fine particles having a particle diameter of 0.001 to 10 μm in the other segment. It is composed of 50 to 99% by weight of a structural type graft copolymer and 1 to 50% by weight of a fatty acid amide formed from a fatty acid having 10 to 25 carbon atoms.

[0011] The graft copolymer composition of the second invention comprises:
In the first invention, the vinyl polymer segment (b) constituting the graft copolymer comprises (meth) acrylic acid,
It is formed from at least one vinyl monomer selected from the group consisting of alkyl (meth) acrylate, glycidyl (meth) acrylate, and a vinyl monomer having a hydroxyl group.

[0012] The graft copolymer composition of the third invention comprises:
In the first or second invention, the graft copolymer suspends an olefin polymer in water, into which at least one vinyl monomer, a radical polymerizable organic peroxide and a radical polymerization initiator are added. Is added, and a vinyl monomer, a radical polymerizable organic peroxide and a radical polymerization initiator are impregnated in the olefin polymer particles, and the vinyl polymer and the vinyl monomer are radically polymerized in the olefin polymer particles. It is obtained by copolymerizing with a volatile organic peroxide, followed by melting and mixing.

[0013] The graft copolymer composition of the fourth invention comprises:
The graft copolymer composition according to any one of the first to third inventions contains a copolymer formed from an α-olefin monomer and another vinyl monomer.

[0014] The thermoplastic resin composition of the fifth invention is characterized in that
The graft copolymer composition 1 according to any one of the first to fourth inventions
-50% by weight, and olefin-based thermoplastic resin 50-99.
% By weight.

[0015] The molded article of the sixth invention is obtained by molding the thermoplastic resin composition of the fifth invention into a predetermined shape.

[0016]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below in detail. The graft copolymer (hereinafter, referred to as graft copolymer (1)) in the present invention is an olefin-based polymer segment (hereinafter, simply referred to as olefin segment).
(A) is used as a trunk component, and a vinyl polymer segment formed from at least one vinyl monomer (hereinafter, simply referred to as a vinyl segment) (b) is used as a branch component. Further, one segment has a multiphase structure type in which a dispersed phase is formed as fine particles having a particle diameter of 0.001 to 10 μm in the other segment.

Here, the olefin polymer forming the olefin segment (a) is a concept including both olefin homopolymers and olefin copolymers. Examples of the olefin polymer as a raw material resin for forming the olefin segment (a) include polypropylene, polyethylene, a copolymer of propylene and an α-olefin having 2 or more carbon atoms, and an α-olefin monomer and a vinyl monomer. And a copolymer with a monomer, an ethylene copolymer rubber, a diene rubber or a polyisobutylene rubber. These can be used alone or in combination of two or more.

Specific examples of the α-olefin having 2 or more carbon atoms include ethylene, 1-butene, 1-pentene, 3-
Methyl-1-butene, 1-hexene, 1-decene, 3-
Methyl-1-pentene, 4-methyl-1-pentene, 1
-Octene and mixtures thereof.

Specific examples of the ethylene copolymer rubber include ethylene-propylene copolymer rubber, ethylene-propylene-diene copolymer rubber, ethylene-butene copolymer rubber and the like.

The intrinsic viscosity [η] of the olefin polymer used as a raw material of the olefin segment (a) (13
(Measured at 5 ° C.) is preferably in the range of 0.1 to 40 dl / g from the viewpoint of the productivity of the olefin polymer.

Next, as the vinyl monomer forming the vinyl segment (b), specifically, for example, styrene,
Methyl styrene, dimethyl styrene, ethyl styrene,
Vinyl aromatic compounds such as isopropylstyrene and chlorostyrene; α-substituted styrenes such as α-methylstyrene and α-ethylstyrene; unsaturated acids such as acrylic acid and methacrylic acid; acrylic acids such as methyl acrylate and ethyl acrylate And acrylates formed from alkyl alcohols having 1 to 20 carbon atoms; methyl methacrylate;
Methacrylic acid such as ethyl methacrylate and C1-20
A methacrylic acid ester formed from an alkyl alcohol; vinyl cyanide such as acrylonitrile and methacrylonitrile; vinyl esters such as vinyl acetate and vinyl propionate; polyethylene glycol acrylate;
Acrylates formed from acrylic acid such as polytetramethylene glycol acrylate and long-chain glycols having a molecular weight of 80 to 6000; methacrylic acid such as polyethylene glycol methacrylate and polytetramethylene glycol methacrylate and having a molecular weight of 80 to 6000 Methacrylic acid esters formed from chain glycols; unsaturated epoxy compounds such as glycidyl methacrylate; 3-hydroxy-1-propene, 4-hydroxy-1-butene;
Compounds having a hydroxyl group such as cis-1,4-dihydroxy-2-butene, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 3-hydroxypropyl methacrylate, 2-hydroxyethyl crotonate;
Maleic acid, fumaric acid, maleic anhydride, maleimide and the like can be mentioned. These can be used alone or in combination of two or more.

Among these, (meth) acrylic acid,
At least one vinyl monomer selected from the group consisting of alkyl (meth) acrylates, glycidyl (meth) acrylate, and vinyl monomers having a hydroxyl group is preferred. This is because these vinyl monomers have a large interaction with the fatty acid amide and easily suppress the surface migration of the fatty acid amide. More specifically, butyl acrylate, methacrylic acid, glycidyl methacrylate, and 2-hydroxypropyl methacrylate are preferred.
In this specification, acrylic and methacryl are collectively referred to as (meth) acryl.

The weight average molecular weight (GPC measurement in THF of styrene conversion) of the vinyl polymer forming the vinyl polymer segment (b) is usually from 1,000 to 2,000.
00,000, preferably 5,000 to 1,200,0
00 range. When the weight average molecular weight is less than 1,000, the heat resistance of the graft copolymer tends to decrease, and when the weight average molecular weight exceeds 2,000,000, the melt viscosity of the graft copolymer is high, Moldability tends to decrease.

As described above, the graft copolymer (1) is of a multi-phase structure type, and the dispersed phase formed by one segment contains particles in a continuous phase (matrix) formed by the other segment. The particles are uniformly dispersed as fine particles having a diameter of 0.001 to 10 μm.

When the particle diameter of the olefin segment (a) or the vinyl segment (b) of the graft copolymer (1) is less than 0.001 μm or more than 10 μm, the olefin-based heat of an olefinic resin such as a thermoplastic elastomer resin is used. Poor dispersibility when blended with a thermoplastic resin, for example, the appearance tends to deteriorate, and the rigidity of the olefin-based thermoplastic resin tends to be impaired.

The graft copolymer (1) has an olefin segment (a) content of usually 5 to 99% by weight, preferably 20 to 95% by weight. Therefore, the content of the vinyl segment (b) is usually 1 to 95% by weight, preferably 5 to 95% by weight.
~ 80% by weight. Olefin segment (a) is 5
If the content is less than 95% by weight or the content of the vinyl segment (b) exceeds 95% by weight, the dispersibility of the graft copolymer in the olefin-based thermoplastic resin tends to decrease, and the appearance of the molded article tends to decrease. Conversely, when the olefin segment (a) exceeds 99% by weight or when the vinyl segment (b) is 1% by weight.
If it is less than 30, the effect of improving the olefinic thermoplastic resin tends to be insufficient.

The melt flow rate (MFR) of the graft copolymer (1) is preferably from 0.01 to 500.
g / 10 min, more preferably 0.1 to 300 g / 10
Min, most preferably from 1 to 200 g / 10 min. The MFR is measured under the conditions of a resin temperature of 230 ° C. and a measurement load of 2.16 kg in accordance with the method specified in JIS 7210. If the MFR is less than 0.01 g / 10 min or exceeds 500 g / 10 min, the compatibility with the olefin-based thermoplastic resin tends to deteriorate, and the appearance of the molded article tends to deteriorate.

The grafting method for producing the graft copolymer (1) may be any of generally known methods such as a chain transfer method and an ionizing radiation irradiation method, and most preferably the following method. Things. This is because the grafting efficiency is high and secondary aggregation due to heat does not occur, so that the expression of performance is more effective and the production method is simple.

That is, the olefin polymer particles 10
0 parts by weight are suspended in water. As a radical polymerizable organic peroxide (compound having a peroxide bond and a radical polymerizable functional group in one molecule) of at least one kind of a vinyl monomer in an amount of 1 to 400 parts by weight, for example, the following general formula ( A)
Or one or a mixture of two or more radically polymerizable organic peroxides represented by the general formula (B)
A radical polymerization initiator having a decomposition temperature of 40 to 90 ° C. for obtaining a half-life of 10 hours or less with respect to 0 parts by weight is a total of a vinyl monomer and a radical polymerizable organic peroxide. A solution consisting of 0.01 to 8 parts by weight per 100 parts by weight is added.

Next, the radical polymerization initiator is heated under conditions that do not substantially decompose, and the vinyl monomer, the radically polymerizable organic peroxide and the radical polymerization initiator are added to the particles of the polyolefin polymer. When the impregnation rate reaches 20% by weight or more, preferably 30% by weight or more of the added amount, the temperature of the aqueous suspension is raised to increase the temperature of the aqueous monomer and the amount of the vinyl monomer and the radical polymerizable organic peroxide. A graft precursor is obtained by copolymerizing an oxide with the olefin-based resin particles. This grafting precursor is used for 100 to 3
By melting and mixing at 00 ° C., a graft copolymer having the olefin segment (a) as a main component and the vinyl segment (b) as a branch component is obtained.

The radically polymerizable organic peroxide represented by the general formula (A) or (B) is the following compound.

[0032]

Embedded image (Wherein, R ₁ is a hydrogen atom or an alkyl group having 1 or 2 carbon atoms, R ₂ is a hydrogen atom or a methyl group, R ₃ and R ₄ are alkyl groups each having 1 to 4 carbon atoms, and R ₅ is a carbon atom having 1 or 2 carbon atoms. Represents an alkyl group, a phenyl group, an alkyl-substituted phenyl group, or a cycloalkyl group having 3 to 12 carbon atoms. M is 1 or 2.) Further, the radical polymerizable compound represented by the general formula (B) Organic peroxides are the following compounds.

[0033]

Embedded image (Wherein, R ₆ is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, R ₇ is a hydrogen atom or a methyl group, R ₈ and R ₉ are each an alkyl group having 1 to 4 carbon atoms, and R ₁₀ is a carbon atom having 1 carbon atom. Represents an alkyl group, a phenyl group, an alkyl-substituted phenyl group or a cycloalkyl group having 3 to 12 carbon atoms, wherein n is 0 or 1.
Or 2. As the radical polymerizable organic peroxide represented by the general formula (A) or (B), specifically preferred are, for example, t-butylperoxyacryloyloxyethyl carbonate; t-butylperoxymethacryloy Roxyethyl carbonate; t-butyl peroxyallyl carbonate; t-butyl peroxymethacrylic carbonate.

The graft copolymer (1) does not necessarily need to use the above-mentioned radical polymerizable organic peroxide. In that case, the obtained graft copolymer (1) and the olefin-based thermoplastic resin are used. Compatibility tends to decrease.

Next, the graft copolymer composition (hereinafter, referred to as graft copolymer composition (3)) is obtained by mixing the graft copolymer (1) obtained as described above or a graft precursor thereof. Fatty acid amide (hereinafter, fatty acid amide (2)
Is melted and mixed.

The fatty acid amide (2) is formed from a fatty acid having 10 to 25 carbon atoms. When the graft copolymer composition (3) is blended with the olefinic thermoplastic resin, Alternatively, the abrasion resistance and scratch resistance of the molded article can be particularly improved. Such effects cannot be exerted with fatty acids having less than 10 carbon atoms. Also, fatty acids having more than 25 carbon atoms are difficult to obtain and are not practical. Specific examples of the fatty acid amide (2) include saturated aliphatic amides such as lauric amide, palmitic amide, stearic amide, and behemic amide; and erucic amide, oleic amide, brassic amide, and elaidic amide. Examples thereof include unsaturated fatty acid amides and bisfatty acid amides such as methylenebisstearic acid amide, methylenebisoleic acid amide, ethylenebisstearic acid amide, and ethylenebisoleic acid amide. These can be used in combination of two or more. Among them, erucamide, oleamide and ethylenebisoleamide are preferably used. In particular, oleic amide, which has the best lubricity among these, is most preferable.

The temperature for producing the graft copolymer composition (3) is preferably from 70 to 250 ° C. If the temperature is lower than 70 ° C., the melting is incomplete or the melt viscosity is high, so that the mixing becomes insufficient, and phase separation or delamination appears, which is not preferable. When the temperature exceeds 250 ° C., the fatty acid amide is undesirably greatly decomposed.

The proportion of the graft copolymer (1) in the graft copolymer composition (3) is preferably 50 to 99% by weight, more preferably 60 to 90% by weight. Therefore, the proportion of the fatty acid amide is preferably 1 to 50% by weight, more preferably 10 to 40% by weight. When the amount of the graft copolymer is less than 50% by weight, the rigidity of the thermoplastic resin composition described below decreases, and when the amount exceeds 99% by weight, the properties tend to be insufficient.

Next, the thermoplastic resin composition is composed of the graft copolymer composition (3) and an olefin-based thermoplastic resin (hereinafter, referred to as an olefin-based thermoplastic resin (4)). Therefore, the thermoplastic resin composition or a molded article thereof is suppressed in bleeding of the fatty acid amide (2) by the graft copolymer composition (3), thereby maintaining a good appearance, and having good scratch resistance and abrasion resistance. And excellent in bending resistance and moldability. As the olefin-based thermoplastic resin (4), an olefin-based polymer which is a raw material resin for forming the olefin segment (a), that is, polypropylene, polyethylene, or polypropylene having 2 carbon atoms is used.
The above-mentioned copolymers with α-olefins, ethylene copolymer rubbers, olefin elastomers and the like are mainly used. If necessary, a rubber and a resin other than the olefin-based thermoplastic resin may be blended. As such a rubber, for example, styrene-butadiene rubber,
Examples thereof include diene rubbers such as nitrile rubber, natural rubber, and butyl rubber (IIR), and polyisobutylene rubber.
Examples of such a resin include a polyester resin such as polyethylene terephthalate.

The above-mentioned olefin-based thermoplastic resin (4) is commercially available, for example, Mirastomer (Mitsui Chemicals, Inc.)
Santoprene (trade name, manufactured by AES Japan KK), Sumitomo TPE (Sumitomo Chemical Co., Ltd.)
Manufactured by Sun Allomer Co., Ltd.
(Product name).

In the graft copolymer composition (3), a copolymer formed from a mixed monomer of an α-olefin monomer and a vinyl monomer (hereinafter referred to as copolymer (5) )). Hereinafter, the graft copolymer composition to which the copolymer (5) is added is referred to as a modified graft copolymer composition. By containing the copolymer (5), the production of the modified graft copolymer composition can be facilitated,
The moldability of the thermoplastic resin composition to which the modified graft copolymer composition has been added can be improved. The content of the copolymer (5) is preferably 1,000% by weight or less based on the above-mentioned graft copolymer composition. When the content of the copolymer (5) exceeds 1000% by weight, the rigidity and heat resistance of the thermoplastic resin composition or a molded article thereof tend to be reduced.

Examples of the α-olefin monomer used for forming the copolymer (5) include ethylene and propylene. As the vinyl monomer, a monomer having a vinyl group copolymerizable with an α-olefin monomer,
For example, a vinyl monomer that can be used when forming the vinyl segment (b) can be used.

As specific examples of the copolymer (5), ethylene-acrylic acid copolymer, ethylene-methyl acrylate copolymer, ethylene-ethyl acrylate copolymer, ethylene-isobutyl acrylate copolymer, ethylene -N-butyl acrylate copolymer, ethylene-ethyl acrylate 2-ethylhexyl copolymer, ethylene-ethyl acrylate-
Examples thereof include a maleic anhydride copolymer, an ethylene-ethyl acrylate-glycidyl methacrylate copolymer, an ethylene-glycidyl methacrylate copolymer, an ethylene-vinyl acetate copolymer or a saponified product thereof. These copolymers can be used alone or in combination of two or more.

The thermoplastic resin composition may be a composition comprising a graft copolymer composition (3) and an olefin thermoplastic resin (4), or a graft copolymer composition (3) and an olefin thermoplastic resin. It is manufactured by melting and mixing the composition comprising (4) and the copolymer (5) at 120 to 250 ° C. When the temperature is lower than 120 ° C., the melting is incomplete or the melt viscosity is high, so that the mixing becomes insufficient, and phase separation or delamination appears, which is not preferable. On the other hand, when the temperature exceeds 250 ° C., the resin and the fatty acid amide are decomposed, which is not preferable. As a method for melting and mixing, known methods such as extrusion kneading and roll kneading are employed.

Further, the graft copolymer composition (3) comprises:
The graft copolymer composition (3) does not necessarily have to be mixed with the olefin-based thermoplastic resin (4). The graft copolymer (1), the fatty acid amide (2) and the olefin-based thermoplastic resin (4) You may mix simultaneously. This is because the graft copolymer (1) and the fatty acid amide (2) are converted into the graft copolymer composition (3) in the olefin-based thermoplastic resin (4). In addition, copolymer (5)
May be previously mixed with the fatty acid amide (2) and then mixed with the olefin-based thermoplastic resin (4). Further, after graft copolymer (1) and copolymer (5) and a part of fatty acid amide (2) are mixed to prepare a master batch, the remaining fatty acid amide (2) and olefin-based thermoplastic resin ( A multi-stage mixing method of mixing 4) is also possible.

Further, the graft copolymer (1) is not necessarily a graft copolymer (1), but may be a fatty acid amide (2),
It does not need to be mixed with the olefin-based thermoplastic resin (4) or the copolymer (5), and may be mixed in the state of the grafting precursor. This is because the grafting precursor is converted into the graft copolymer (1) by melting and mixing. In addition, when melting and mixing with the grafting precursor,
Some of them may be copolymerized with the fatty acid amide (2), the olefin-based thermoplastic resin (4) or the copolymer (5) to form a graft copolymer, but this is not a problem.

The proportion of the graft copolymer composition (3) in the thermoplastic resin composition is preferably 1 to 50% by weight, more preferably 2 to 30% by weight. Therefore, the proportion of the olefinic thermoplastic resin (4) is 50 to 9%.
It is preferably 9% by weight, more preferably 70-98% by weight. When the amount of the graft copolymer composition (3) is less than 1% by weight, the characteristics of the graft copolymer are insufficiently developed, and when the amount exceeds 50% by weight, the rigidity and heat resistance of the molded article decrease. Is not preferred.

The proportion of the fatty acid amide (2) in the thermoplastic resin composition is preferably from 0.01 to 10% by weight, more preferably from 0.1 to 8% by weight. When the amount of the fatty acid amide (2) is less than 0.01% by weight, the properties based on the fatty acid amide (2) are not sufficiently exhibited. And the appearance of the molded article is deteriorated, which is not preferable.

Further, the thermoplastic resin composition may contain a copolymer (5). The proportion of the copolymer (5) in the thermoplastic resin composition is preferably 50% by weight or less, more preferably 30% by weight or less. When the amount of the copolymer (5) exceeds 50% by weight, the rigidity and heat resistance of the thermoplastic resin composition tend to decrease. Further, since the copolymer (5) does not have a special multiphase structure, bleeding of the fatty acid amide (2) cannot be controlled, and the appearance of the molded article tends to be poor.

The thermoplastic resin composition of the present invention may further comprise a flame retardant such as a halogen-containing compound such as halogenated styrene or a phosphorus compound, carbon fiber or mica, if necessary, without departing from the gist of the present invention. Reinforcing fillers such as talc, antioxidants such as phenols, lioethers, and phosphorus, stabilizers, lubricants, dispersants, foaming agents, crosslinking agents, UV inhibitors, coloring agents, and mineral oil softeners. It can be contained.

A molded article can be obtained by molding the above-mentioned thermoplastic resin composition into a predetermined shape. As the molding method of the thermoplastic resin composition, it is possible to mold with a commonly used thermoplastic resin molding machine, and it is possible to use a calendering method, a pressure forming method, a thermoforming method, a blow molding method, a foam molding method. , Extrusion molding, injection molding, and vacuum molding.

Examples of the molded article include a sheet, a film, a thermoformed article, a hollow molded article, a foam, and an injection molded article. Further, there may be mentioned a laminate obtained by laminating a urethane-based thermoplastic elastomer on the above-mentioned molded product, and a multilayer molded film obtained by gravure-printing a urethane paint. Specific examples of the molded body include, for example, a weather strip for a vehicle and a skin material for molding.

The effects exerted by the above embodiments will be summarized below. The graft copolymer in the graft copolymer composition has an olefin segment (a)
And the vinyl segment (b) form a dispersed phase as fine particles. For this reason, the compatibility between the graft copolymer and the fatty acid amide is good, and the interaction is excellent. As a result, the surface migration of the fatty acid amide can be suppressed.

The vinyl segment (b) is (meth)
Acrylic acid, alkyl (meth) acrylate,
By being formed from at least one vinyl monomer selected from the group consisting of glycidyl (meth) acrylate and a vinyl monomer having a hydroxyl group, the interaction with a fatty acid amide is increased. be able to.

When the graft copolymer is obtained by the method of passing through a grafting precursor, the graft efficiency can be increased, the graft copolymer can be easily obtained, and the secondary Agglomeration can be avoided and performance can be more effectively expressed.

Since the modified graft copolymer composition contains the copolymer (5) in an amount of not more than 1000% by weight based on the graft copolymer composition (3), the modified graft copolymer composition When the polymer composition is added to the olefin-based thermoplastic resin, the production of the modified graft copolymer composition or the thermoplastic resin composition can be facilitated, and the moldability of the thermoplastic resin composition can be improved. Can be improved.

The thermoplastic resin composition obtained by adding the graft copolymer composition (3) to the olefin-based thermoplastic resin (4) is characterized by the properties of the graft copolymer (1) and the olefin segment (a) Has excellent compatibility with the olefin-based thermoplastic resin (4), and prevents interfacial peeling. For this reason, the thermoplastic resin composition or a molded article thereof can suppress the bleeding of the fatty acid amide (2) in the graft copolymer (1), maintain a good appearance, and have good scratch resistance and abrasion resistance. And excellent in bending resistance and moldability.

A molded article obtained by molding the above-mentioned thermoplastic resin composition can maintain good appearance for a long period of time, has good scratch resistance and abrasion resistance for a long period of time, and has excellent bending resistance. . Therefore, in particular, a molded article using an olefin-based thermoplastic elastomer requires flexibility such as automobile parts, home appliance parts, miscellaneous goods, etc., taking advantage of the fact that it can be processed by an ordinary thermoplastic resin molding machine. It can be used in a wide range of fields.

[0059]

EXAMPLES Hereinafter, the above embodiment will be described in more detail by reference examples, examples and comparative examples, but the present invention is not limited to these embodiments. The test methods used for measuring physical properties in these Reference Examples, Examples and Comparative Examples are as follows. (1) Melt flow rate (MFR): JIS K using a melt indexer (manufactured by Toyo Seiki Seisaku-sho, Ltd.)
According to the method according to 7210, Reference Examples 1 to 3 were measured at a temperature of 230 ° C. and a load of 2.16 kg.
Comparative Examples 1 to 5 and 7 to 10 have a measurement temperature of 230 ° C. and a load of 10
In Example 17 and Comparative Example 6, the measurement temperature was 190 ° C. and the load was 2.16 kg. (2) Hardness: Examples 7 to 15, Comparative Examples 1 to 4, 7 to 9
Was based on JIS K 6301, Example 16, Comparative Examples 5 and 10 were based on JIS K 6758, and Example 17 and Comparative Example 6 were based on JIS K 7215. (3) Bleed resistance: 3 mm in thickness, 90 mm on a side from pellets using an injection molding machine (manufactured by Tabata Machine Industry Co., Ltd.)
, And the plate was left in an oven at 70 ° C. for 72 hours, and fatty acid amide bleeding on the plate surface was visually observed and evaluated according to the following evaluation criteria. ：: No bleed at all. Δ: Slight bleed. ×: There is bleeding ××: There is severe bleeding. (4) Abrasion resistance: A 700 g load was applied to the same square plate test piece as the test piece used in the bleed resistance test using a gakushin-type fastness friction and wear tester, and 100 g of Kanakin No. 3 cloth was used. The surface of the test piece after repeated reciprocating wear was visually observed and evaluated according to the following evaluation criteria. ：: scar is scarcely seen. Δ: Scars are slightly conspicuous. ×: The scar is large and conspicuous. XX: The scar is conspicuous, and a large amount of powdery wear powder is generated. (5) Scratch resistance: A tapered scratch tester (manufactured by Toyo Seiki Seisaku-sho) was used on the same square plate test piece as the test piece used in the bleed resistance test, and the cutting edge was 3.5 cm from the center of rotation. Attach a blade so that
With the turntable rotated at a speed of 0.5 rpm, a 0.5 N load was applied to the blade to scratch the test piece.
The scratch was evaluated according to the following evaluation criteria. ：: scar is scarcely seen. Δ: Scars are slightly conspicuous. ×: The scar is large and conspicuous. (6) Creases: The same square plate test piece as the test piece used in the bleed resistance test was bent three times at 180 degrees, and the wrinkles were observed and evaluated according to the following evaluation criteria. ：: Almost no wrinkles are seen. Δ: Some wrinkles are observed. ×: Creases are clearly seen.

Abbreviations in the following Reference Examples and Tables represent the following substances. TPO-1: Olefin-based thermoplastic elastomer (trade name: Mirastomer 8030, manufactured by Mitsui Chemicals, Inc.) TPO-2: Olefin-based thermoplastic elastomer (trade name: Sumitomo TPE3885, manufactured by Sumitomo Chemical Co., Ltd.) TPO-3: Olefin-based thermoplastic elastomer (trade name: Mirastomer 5030, manufactured by Mitsui Chemicals, Inc.) TPO-4: Olefin-based thermoplastic elastomer (trade name: Santoprene 201-87, manufactured by AES Japan Ltd.) PE : Polyethylene (trade name: Sumikasen G401, manufactured by Sumitomo Chemical Co., Ltd.) PP: Polypropylene (trade name: Sun Allomer PB67)
1A, manufactured by Sun Allomer Co., Ltd.) EPR: ethylene-propylene copolymer (trade name: EP
07P, manufactured by Nippon Synthetic Rubber Co., Ltd.) EEA: Ethylene-ethyl acrylate copolymer (trade name: Lexlon A4200, Nippon Polyolefin Co., Ltd.)
MMA: Methyl methacrylate MAA: Methacrylic acid HPMA: 2-Hydroxypropyl methacrylate BA: Butyl acrylate St: Styrene AN: Acrylonitrile GMA: Glycidyl methacrylate (Reference Example 1, Production of graft copolymer (1)) Pure water 2500 in a 5 liter stainless steel autoclave
g of polyvinyl alcohol and 2.5 g of polyvinyl alcohol as a suspending agent. 700 g of EPR was put in this, stirred and dispersed.

Separately, di-radical polymerization initiators
3,5,5-trimethylhexanoyl peroxide
5 g, 9 g of t-butyl peroxymethacryloyloxyethyl carbonate as a radical polymerizable organic peroxide, 100 g of St as a vinyl monomer, 100 g of BA,
The solution was dissolved in 100 g of HPMA, and the solution was charged into the autoclave and stirred.

Next, the temperature of the autoclave was raised to 60 to 65 ° C., and the mixture was stirred for 3 hours to impregnate the radical polymerization initiator, the radically polymerizable organic peroxide and the vinyl monomer into the EPR. Subsequently, after confirming that the total amount of the impregnated vinyl monomer, the radical polymerizable organic peroxide and the radical polymerization initiator is 30% by weight or more of the added amount, the temperature is reduced to 70 to 75%. C. and maintained at that temperature for 6 hours to complete the polymerization, washed with water and dried to obtain a grafted precursor.

The styrene-butyl acrylate-hydroxypropyl methacrylate copolymer was extracted from the grafted precursor with tetrahydrofuran, and the weight average molecular weight (GPC measurement in THF, styrene conversion) was measured by GPC. 000.

Then, the grafted precursor was subjected to a Labo Plastomill single screw extruder (manufactured by Toyo Seiki Seisaku-sho, Ltd.) for 18 hours.
It was extruded at 0 ° C. and subjected to a grafting reaction to obtain a graft copolymer (1).

When the graft copolymer (1) was observed with a scanning electron microscope (manufactured by Hitachi, Ltd.),
It was a thermoplastic resin having a multiphase structure in which true spherical resins having a particle diameter of 0.3 to 0.4 μm were uniformly dispersed. At this time, the graft efficiency of the styrene-butyl acrylate-hydroxypropyl methacrylate copolymer was 55% by weight. (Reference Example 2) In a stainless steel autoclave having a capacity of 5 liters, 2500 g of pure water was added, and 2.5 g of polyvinyl alcohol was further dissolved as a suspending agent. 900 g of PE was put therein, and stirred and dispersed.

Separately, 0.5 g of benzoyl peroxide as a radical polymerization initiator, 3 g of t-butylperoxymethacryloyloxyethyl carbonate as a radical polymerizable organic peroxide, and MMA40 as a vinyl monomer.
g, 20 g of BA and 40 g of MAA were dissolved in a monomer mixture, and this solution was charged into the autoclave and stirred.

Then, the temperature of the autoclave was raised to 60 to 65 ° C., and the mixture was stirred for 2 hours to obtain a radical polymerization initiator.
Radical polymerizable organic peroxide and vinyl monomer
Impregnated inside. Then, after confirming that the total amount of the impregnated vinyl monomer, radically polymerizable organic peroxide and radical polymerization initiator is 30% by weight or more of the added amount, the temperature is raised to 80 to 85 ° C. The temperature was raised for 5 hours to complete the polymerization, washed with water and dried to obtain a graft precursor.

A methyl methacrylate-butyl acrylate-methacrylic acid copolymer was extracted from the grafted precursor with tetrahydrofuran (THF), and the weight average molecular weight (measured in THF, styrene conversion) was measured by GPC. 800,000.

The grafting precursor was subjected to a Labo Plastomill single screw extruder (manufactured by Toyo Seiki Seisaku-sho, Ltd.) for 20 minutes.
It was extruded at 0 ° C. and subjected to a grafting reaction to obtain a graft copolymer (1).

When the graft copolymer (1) was observed with a scanning electron microscope (manufactured by Hitachi, Ltd.),
It was a thermoplastic resin having a multiphase structure in which true spherical resins having a particle diameter of 0.2 to 0.3 μm were uniformly dispersed. At this time, the graft efficiency of the methyl methacrylate-butyl acrylate-methacrylic acid copolymer was 90% by weight. (Reference Example 3) The graft copolymer (1) was obtained in the same manner as in Reference Example 1, except that the components and ratios shown in Table 1 were changed.

[0071]

[Table 1] (Reference Example 4) 80 parts by weight of EEA as a copolymer (5) and oleic amide 20 as a fatty acid amide (2)
After dry blending with parts by weight, cylinder temperature is 16
Pellets were obtained by kneading with a coaxial twin screw extruder having a screw diameter of 30 mm set at 0 ° C. (Examples 1 to 6, Production of Graft Copolymer Composition (3)) Grafting precursor or graft copolymer (1) and fatty acid amide (2) or copolymer in the components and ratios shown in Table 2 After dry-blending EEA as (5), the mixture was melted and mixed by a coaxial twin-screw extruder having a screw diameter of 30 mm set at a cylinder temperature of 180 ° C., and pellets of the graft copolymer composition (3) were obtained. Obtained.

[0072]

[Table 2] (Examples 7 to 12, Production of Thermoplastic Resin Composition) Graft copolymer composition (3) with components and proportions shown in Table 3
After dry-blending the olefin-based thermoplastic resin (4), the mixture was melted and mixed by a coaxial twin-screw extruder having a screw diameter of 30 mm and a cylinder temperature of 180 ° C to obtain pellets of the thermoplastic resin composition. Table 3 shows the results of the various physical property tests.

[0073]

[Table 3] (Examples 13 to 15, Production of Thermoplastic Resin Composition) Table 4
In the same manner as in Example 8, pellets of a thermoplastic resin composition containing the olefin-based thermoplastic resin (4) were obtained by multi-stage melting and mixing with the components and ratios shown in (1). Table 4 shows the results of the various physical property tests.

[0074]

[Table 4] (Examples 16 to 17, Production of Thermoplastic Resin Composition) Table 5
In the same manner as in Example 8, pellets of a thermoplastic resin composition containing the olefin-based thermoplastic resin (4) were obtained by multi-stage melting and mixing with the components and ratios shown in (1). Table 5 shows the results of various physical property tests.

[0075]

[Table 5] (Comparative Examples 1 to 6) These comparative examples use the olefin-based thermoplastic resin (4) alone used in the examples. (Comparative Examples 7 to 10) Pellets were obtained by melting and mixing the components and ratios shown in Table 6 as an olefin-based thermoplastic resin composition containing no graft copolymer (1). Table 6 shows the results of the various physical property tests.

[0076]

[Table 6] As shown in Table 6, the olefin-based thermoplastic resins of Comparative Examples 1 to 6 cannot obtain good wear resistance and scratch resistance. Further, in Comparative Examples 7 to 10 in which oleic amide was used for improving wear resistance and scratch resistance, although the wear resistance and scratch resistance were improved, the bleeding of oleic amide could not be controlled. It became clear that the bleeding property and the appearance of the molded article were extremely deteriorated.

On the other hand, as shown in Tables 3 to 5, when the graft copolymer composition of the present invention was used, Examples 7 to 1 were used.
As can be seen from the results of No. 7, good abrasion resistance and scratch resistance were obtained, and at the same time, good results of bleed resistance were obtained. Also, the MFR is higher than Comparative Examples 1 to 6,
Examples 7 to 17 were excellent, and it was clear that the moldability was excellent.

The present invention may be implemented by changing the configuration of the embodiment as follows. A part of the graft copolymer (1), the olefin-based thermoplastic resin (4) and the fatty acid amide (2) is mixed to prepare a master batch, and the remaining fatty acid amide (2) and the copolymer (5) are mixed. ) Is also possible. In addition, a part of the target thermoplastic resin composition may be used as a master batch.

A masterbatch may be prepared using a grafting precursor as the graft copolymer (1). -In addition to the olefin-based thermoplastic resin, other thermoplastic resins may be appropriately mixed in the thermoplastic resin composition according to the purpose.

The technical ideas grasped from the above embodiment will be described below. The vinyl monomer is butyl acrylate, methacrylic acid, glycidyl methacrylate or methacrylic acid 2-
The graft copolymer composition according to claim 2, which is hydroxypropyl. With such a configuration, the effect of claim 2 can be further improved.

The graft copolymer composition according to any one of claims 1 to 4, wherein the graft copolymer has a melt flow rate (MFR) of 0.01 to 500 g / 10 minutes. With such a configuration, the moldability of a thermoplastic resin composition in which the graft copolymer composition is blended with an olefin-based thermoplastic resin can be improved.

[0082]

As described above, according to the present invention, the following effects can be obtained. According to the graft copolymer composition of the first invention, the interaction with the fatty acid amide is excellent.

According to the graft copolymer composition of the second invention, in addition to the effects of the first invention, the interaction with the fatty acid amide can be increased, and the surface migration of the fatty acid amide can be suppressed.

According to the graft copolymer composition of the third invention, in addition to the effects of the first or second invention, the graft efficiency can be increased, the graft copolymer can be easily obtained, and the thermal conductivity can be improved. Secondary agglomeration can be avoided,
The performance can be more effectively expressed.

According to the graft copolymer composition of the fourth invention, in addition to the effects of any of the first to third inventions, the graft copolymer composition or the thermoplastic resin composition to which the graft copolymer composition has been added is added. The production can be facilitated, and the moldability of the thermoplastic resin composition can be improved.

According to the thermoplastic resin composition of the fifth invention, bleed is suppressed, the appearance is maintained well, scratch resistance and abrasion resistance are good, and bending resistance and moldability are excellent. I have.

According to the molded article of the sixth invention, good appearance can be maintained, scratch resistance and abrasion resistance are good, and bending resistance is excellent. Therefore, in particular, a molded article using an olefin-based thermoplastic elastomer requires flexibility such as automobile parts, home appliance parts, miscellaneous goods, etc., taking advantage of the fact that it can be processed by an ordinary thermoplastic resin molding machine. It can be used in a wide range of fields.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C08L 23/00 C08L 51:06 // (C08L 23/00 B60J 5/00 501L 51:06) (72) Inventor Norihisa Yamada 18-2 Higashiobori, Kagiya-cho, Tokai-shi, Aichi (72) Inventor Masumi Takamura 5-4-6, Hanazono-cho, Handa-shi, Aichi (72) Inventor Motoyuki Sugiura 102F, Fukuda, Minowa-cho, Anjo, Aichi Terms (reference) 3D201 AA24 BA01 CA19 CA20 EA28 EA29 4F071 AA14 AA15 AA77 AC09 AE12 AF17 AF22 AF25 AF53 AF55 AH19 BA01 BB03 BB04 BB05 BB06 BC01 BC02 BC04 BC07 4J002 BB011 BB021 BB051 BB071 BB071 BB071 BB071 AA14 AA68 AA69 AA72 AC01 AC02 AC32 AC33 BA05 BA06 BA08 BA19 BA20 BA25 BA27 BA30 BA31 BA32 BA34 BA35 BA50 BB03 BB04 CA10 DB08 DB10 DB15 DB22 DB25 FA01 FA06 GA01 GA02 GA06 GA08

Claims (6)

[Claims] 1. A olefin polymer segment (a) as a trunk component, and a vinyl polymer segment (b) formed from at least one vinyl monomer as a branch component.
One segment has a particle size of 0.0 in the other segment.
50 to 99% by weight of a multiphase structure type graft copolymer forming a dispersed phase as fine particles of 01 to 10 µm;
A graft copolymer composition comprising 1 to 50% by weight of a fatty acid amide formed from a fatty acid having 10 to 25 carbon atoms. 2. A vinyl monomer having a vinyl polymer segment (b) constituting a graft copolymer, comprising (meth) acrylic acid, alkyl (meth) acrylate, glycidyl (meth) acrylate, and a hydroxyl group. The graft copolymer composition according to claim 1, wherein the graft copolymer composition is formed from at least one vinyl monomer selected from the group consisting of a polymer. 3. A graft copolymer comprising an olefin polymer suspended in water and a solution comprising at least one vinyl monomer, a radically polymerizable organic peroxide and a radical polymerization initiator. In addition, a vinyl monomer, a radical polymerizable organic peroxide and a radical polymerization initiator are impregnated into the olefin polymer particles, and the vinyl monomer and the radical polymerizable organic peroxide are impregnated in the olefin polymer particles. 3. The graft copolymer composition according to claim 1, wherein the graft copolymer composition is obtained by melting and mixing after copolymerizing the product. 4. A copolymer formed from an α-olefin monomer and another vinyl monomer with respect to the graft copolymer composition according to any one of claims 1 to 3. A graft copolymer composition containing 5. A thermoplastic resin composition comprising 1 to 50% by weight of the graft copolymer composition according to any one of claims 1 to 4 and 50 to 99% by weight of an olefin-based thermoplastic resin. object. 6. A molded product obtained by molding the thermoplastic resin composition according to claim 5 into a predetermined shape.