JPH09255836A - Vinyl chloride resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject composition comprising a vinyl chloride polymer and glass fibers coated with a specific resin and remarkably improved in strength, impact resistance, elastic modulus, water resistance, surface appearance and moldability. SOLUTION: This vinyl chloride resin composition comprises (A) 100 pts.wt. of a vinyl chloride polymer and (B) glass fibers coated with a coating resin obtained by melting (i) a polymer miscible with the component A, (ii) a crystalline polymer immiscible with the component A and (iii) a peroxide. Further, (iv) a monomer for improving the adhesivity of the glass fibers and (v) a copolymer simultaneously having a polymer chain immisicible with the component A and a polymer chain miscible with the component A in the same molecule. The component (i) is preferably acrylonitrile-styrene copolymer or polymethyl methacrylate, and the component (ii) is preferably polypropylene having a crystal melting point of >=250 deg.C.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to strength, impact resistance,
Gives a molded product with excellent elastic modulus, water resistance, surface appearance, etc.
It also relates to a vinyl chloride resin composition having excellent moldability.

[0002]

2. Description of the Related Art A vinyl chloride resin composition containing a vinyl chloride resin or a plasticizer added thereto has relatively high mechanical strength and can be manufactured at low cost.
Therefore, it is used as a resin material for producing general-purpose molded products in a wide range of applications such as building members, industrial members, and electric equipment members. However, depending on the application, heat resistance,
It has the drawback of being inferior in mechanical strength, dimensional stability and thermal expansion.

In order to solve these drawbacks, it has been studied to alloy polymers having different properties with each other to improve the properties of the resin. For example, various proposals have been made for alloying a vinyl chloride resin and an olefin resin (Japanese Patent Publication No. S60-36178, JP-A No. 63-60).
4039, JP-A-1-165640, and JP-A-2-199.
127, JP-A-2-199128, and JP-A-2-1991.
29). However, since this alloyed resin uses an olefin resin, its elastic modulus and heat resistance are insufficient.

On the other hand, it is known that glass fibers are filled and blended with a vinyl chloride resin to enhance and improve its characteristics. This method generally improves rigidity and tensile strength considerably, but often reduces impact strength.

In particular, vinyl chloride resins are inferior in melt flow characteristics to other thermoplastic resins, so that wetting with glass fibers is poor, glass fibers are not uniformly dispersed, and chlorides containing glass fibers are mixed. As a result of the melt flow characteristics of the vinyl resin being significantly deteriorated, damage to the glass fiber during kneading,
There is a drawback in that the resin is thermally deteriorated and the impact strength is particularly poor. Furthermore, since glass fibers are raised on the surface of the molded product and the surface becomes rough, the surface appearance is inferior and desired properties cannot be easily obtained.

In order to solve the above drawbacks, for example, (1)
Method for increasing molding processing temperature, (2) Resin having excellent fluidity and miscibility with lubricant, surface modifier or vinyl chloride resin, for example, ethylene-vinyl acetate copolymer, ethylene-vinyl chloride copolymer It has been proposed to add a chlorinated polyethylene or the like to reduce the viscosity of the vinyl chloride resin, improve the wettability with the glass fiber and improve the dispersibility.

However, in the method (1) of increasing the molding temperature, since the molding temperature and the decomposition temperature of the vinyl chloride resin are originally close to each other, strict temperature control is required and it is not practical. However, a slight temperature rise causes decomposition of the resin, and the mechanical strength of the molded product decreases.

In the method (2) of adding a resin for decreasing the viscosity of a vinyl chloride resin, a large amount of resin must be added in order to obtain a desired viscosity level, and the inherent properties of the vinyl chloride resin are remarkably increased. Therefore, there is a drawback that the advantage of improving the mechanical strength of the resin by adding the glass fiber is offset.

Further, in order to avoid breakage of the glass fiber generated at the time of molding and to improve the mechanical strength of the molded product,
It is known to add glass fibers from the extruder vent holes or die sections. According to this method, the glass fiber is not damaged, but the wettability between the resin and the glass fiber is not sufficient, so that the mechanical strength, especially the water resistance is significantly impaired.

Further, in order to improve these drawbacks,
(1) Japanese Patent Publication No. Sho 49-6830, Japanese Patent Publication No. Sho 49-1320
9, JP-B-49-27663, vinyl monomers such as vinyl chloride, vinyl acetate, and vinyl aromatic compounds are polymerized in the presence of glass fibers, and the glass fibers are coated with a polymer composed of the monomers, A method of kneading and mixing the polymer-coated glass fiber and a vinyl chloride resin to obtain a molded article is proposed. Further, (2) Japanese Patent Application Laid-Open No. 6-65427 proposes a method of improving the properties of an alloy resin by adding a compatibilizer.

However, according to these methods, the adhesion between the resin and the glass fiber is improved, and although some improvements in the appearance of the molded product and various mechanical strengths are recognized, impact resistance, elastic modulus and water resistance are improved. Also, the balance of moldability is poor, and it is not always satisfactory. Further, since these methods use a monomer and involve a batch-type polymerization reaction, it takes time to manufacture and continuous production is not possible, which is economically problematic. There are also restrictions and disadvantages.

[0012]

The present invention solves the above-mentioned drawbacks of the prior art and provides a vinyl chloride resin composition having excellent mechanical strength such as moldability and impact resistance, and excellent surface appearance. To do.

[0013]

Means for Solving the Problems As a result of intensive studies by the present inventors, a component consisting of a polymer miscible with a vinyl chloride polymer, a polymer immiscible with a vinyl chloride polymer and a peroxide. Vinyl chloride resin blended with glass fiber coated with resin obtained by melting is improved in mechanical strength such as impact resistance, strength, elastic modulus and water resistance, and surprisingly, moldability , And found that the surface appearance is significantly improved. The present invention is the following invention, which has this as its gist.

100 parts by weight of the vinyl chloride polymer (A), a polymer (a) which is miscible with the vinyl chloride polymer, and a crystalline polymer (b) which is immiscible with the vinyl chloride polymer. ) And a glass fiber (B) 1 coated with a coating resin obtained by melting a component containing peroxide (c) 1
A composition comprising 0 to 200 parts by weight.

The coating resin is a monomer (d) for improving the adhesion between the above-mentioned polymer (a), polymer (b) and peroxide (c) and further glass fiber, or a vinyl chloride-based heavy polymer. A resin obtained by melting a component containing a copolymer (e) having a polymer chain (X) immiscible with the polymer and a polymer chain (Y) miscible with the vinyl chloride polymer in the same molecule. The above composition.

[About vinyl chloride polymer (A)] The vinyl chloride polymer (A) used in the present invention can be obtained by a known production method, that is, a suspension polymerization method, an emulsion polymerization method, or a bulk polymerization method. The vinyl chloride polymer (A) preferably has an average degree of polymerization in the range of 400 to 1500, and 450 to
Those of 1000 are particularly preferable. If the average polymerization degree is too small, the mechanical properties such as impact resistance and elastic modulus and the thermal stability are lowered, which is not preferable. On the other hand, if the average degree of polymerization is too large, the melt fluidity is remarkably reduced and molding becomes too difficult, which is not preferable.

The vinyl chloride polymer (A) referred to here is substantially a vinyl chloride polymer in which 60% by weight or more of the constituent components are composed of polymerized units based on vinyl chloride. means. Specifically, vinyl chloride homopolymer, ethylene-vinyl chloride copolymer, vinyl acetate-
Vinyl chloride copolymer, ethylene / vinyl acetate copolymer
Examples thereof include a graft copolymer of a vinyl chloride polymer, and also include post-chlorinated polyvinyl chloride. These may be used alone or in combination of two or more.

[Regarding Polymer (a) Miscible with Vinyl Chloride Polymer (A)] The term "miscible" as used herein means that it is miscible with the vinyl chloride polymer (A) in a thermodynamically stable state. It means a property in which a polymer is mixed in a molecular order, or some affinity is exerted on the interface to form a stable microphase-separated state. Therefore, when the polymer (a) is the vinyl chloride polymer (A), the mixture is substantially uniformly mixed. Further, the polymer (a) is a vinyl chloride polymer (A)
When the vinyl chloride polymer (A) has a certain degree of miscibility with the continuous layer of the vinyl chloride polymer (A), for example, a particle size of 0.01 to 10 μm
m can be stably dispersed in a particle state.

That is, when the coated glass fiber containing the polymer (a) is blended with the vinyl chloride polymer (A) and melt-kneaded, the glass fiber is rapidly mixed with the vinyl chloride polymer (A). In addition, since the interface with the vinyl chloride polymer (A) which is the matrix has an affinity, it has the effect of significantly improving the mechanical strength such as impact resistance, strength, elastic modulus and water resistance. It can be demonstrated.

The molecular weight of the polymer (a) is not particularly limited, but if the molecular weight is too large, the kneadability with other components becomes insufficient, which is not preferable, and the average molecular weight is 1000 to 4000.
00 is preferable.

In the following, vinyl chloride polymer (A)
A monomer that is a non-miscible homopolymer is called a monomer (m), and a monomer that is a homopolymer that is miscible with a vinyl chloride polymer (A) is a monomer (n). Say. Further, a unit derived from the monomer and constituting the polymer is called a polymerized unit, and a polymerized unit derived from the monomer (m) is a polymerized unit (m);
The polymerization unit derived from the monomer (n) is referred to as a polymerization unit (n). Further, specific names of the polymerized units are referred to by adding “polymerized units” to the names of the monomers (for example, “propylene polymerized units”).

The polymer (a) contains a polymer unit (n) which is miscible with the vinyl chloride polymer (A),
As long as the polymer (a) as a whole is miscible with the vinyl chloride polymer (A), it may contain other polymerized units. Examples of other polymerized units include those other than the polymerized unit (n) and the polymerized unit (m), and those hardly distinguishable from any of them. The polymer (a) may be composed of two or more types of polymerized units (n), and the same applies to a case where the polymer (a) has a polymerized unit (m) or another polymerized unit.

Monomers (n) include vinyl chloride monomers, acrylic acid-based monomers such as acrylic acid alkyl ester-based monomers, and methacrylic acid-based monomers such as methacrylic acid alkyl ester-based monomers. Body, vinyl cyanide-based monomer and the like.

The vinyl cyanide-based monomer forms a polymer having a high miscibility with the vinyl chloride-based polymer (A), but the polymer alone is insufficient in physical properties, so that other monomer is used. It is preferred to copolymerize with the body to form polymer (a).

As a specific example of the polymer (a), the above-mentioned vinyl chloride polymer (A) may be used, a copolymer of a vinyl cyanide monomer and an aromatic vinyl monomer, an alkyl acrylate. It may be an ester polymer, an alkyl methacrylate ester polymer, a vinyl acetate polymer, or the like.

More specifically, as a copolymer of a vinyl cyanide-based monomer and an aromatic vinyl-based monomer, vinyl cyanide-based monomers such as acrylonitrile and methacrylonitrile and styrene and α- A copolymer formed by copolymerizing monomers in combination with aromatic vinyl monomers such as methylstyrene, vinyltoluene, and chlorostyrene. The vinyl cyanide monomer in the copolymer is The proportion of the polymerized units based on this is preferably 5 to 80% by weight, and particularly preferably 10 to 50% by weight.

When the ratio of vinyl cyanide-based polymer units is low, the miscibility with the vinyl chloride-based polymer (A) is poor and the vinyl chloride-based polymer (A) as a matrix cannot be sufficiently dispersed, The mechanical strength of the obtained molded article is lowered, and the affinity with the glass fiber is not sufficient, so that the water resistance of the obtained molded article is deteriorated, which is not preferable. Particularly preferred copolymers are acrylonitrile-
It is a styrene copolymer.

As the acrylic acid alkyl ester-based polymer and the methacrylic acid alkyl ester-based polymer, a polymer of a monomer having an alkyl moiety having 4 or less carbon atoms is preferable. When the number of carbon atoms in the alkyl portion is 5 or more, the polymer becomes poor in miscibility with the vinyl chloride polymer (A), which is not preferable for the same reason as described above. Particularly, a methacrylic acid alkyl ester monomer is preferable.

One or more of the methacrylic acid alkyl ester-based monomers, a combination of the methacrylic acid alkyl ester-based monomer and another methacrylic acid alkyl ester-based monomer, the methacrylic acid alkyl ester-based monomer And a monomer other than the alkyl methacrylate ester-based monomer are preferred. Specifically, polymethyl acrylate, polymethyl methacrylate, polyethyl acrylate,
And polyethyl methacrylate. A particularly preferred polymer is polymethyl methacrylate.

Examples of vinyl acetate polymers include vinyl acetate homopolymers and ethylene-vinyl acetate copolymers. For ethylene-vinyl acetate copolymers, the proportion of polymerized units based on vinyl acetate monomer is 10%. It is preferably at least wt%. When the amount is less than 10% by weight, the miscibility with the vinyl chloride polymer (A) becomes poor, which is not preferable for the same reason as above.

Among the polymers (a), those having a higher glass transition temperature than the vinyl chloride polymer (A) are more preferable from the viewpoint of heat resistance represented by the heat distortion temperature when blended with the vinyl chloride resin. Acrylonitrile-styrene copolymer or polymethylmethacrylate is particularly preferred.

[Crystalline Polymer (b) Immiscible with Vinyl Chloride Polymer (A)] The polymer (b) is
It has no affinity at the interface with the vinyl chloride polymer (A), has the property of not being able to form a stable microphase separation state, and exhibits crystallinity. The crystallinity as referred to herein means a clear crystal melting point, for example, a substance showing an endothermic peak by a thermal analysis method such as DSC, and having a property that the melt viscosity is rapidly lowered at the temperature, and is not necessarily a crystallization. 100%
Does not mean

The crystalline melting point is preferably 250 ° C. or lower, which is close to the processing temperature of the vinyl chloride polymer (A), and particularly preferably 200 ° C. or lower. Furthermore, from the viewpoints of mechanical strength and heat resistance, the lower limit is preferably a glass transition temperature higher than that of the vinyl chloride polymer (A), and is preferably 80 ° C or higher, particularly preferably 100 ° C or higher.

When the coated glass fiber is blended with the vinyl chloride polymer (A) and melt-kneaded, the polymer (b) portion in the coating resin is essentially vinyl chloride polymer (A).
Since it has no miscibility, it exhibits a so-called lubricating property of slipping on the molecular chain of the vinyl chloride polymer (A) without being entangled with the molecular chain. In particular, it is remarkable when the crystal melting point is lower than the processing temperature. Therefore, the melt viscosity of the system can be reduced, and the effect of significantly improving the moldability and surface appearance can be exhibited, and the shearing force generated by kneading can be reduced. Improve.

The molecular weight of the polymer (b) is not particularly limited, but if the molecular weight is too large, the kneadability with other components will be insufficient, which is not preferable, and the average molecular weight of 1000 to 4000.
00 is preferable.

The polymer (b) contains a polymer unit (m), but as long as the polymer (b) is immiscible with the vinyl chloride polymer (A) as a whole, the polymer unit (n) and other The polymerized units of may be included. The polymerization unit (m) is not limited as long as it is a polymerization unit that is substantially immiscible with the vinyl chloride polymer (A). For example, a homopolymer of ethylene, propylene, another α-olefin, or a homopolymer thereof may be used. Examples include a combination of monomers. Specifically, polyethylene and polypropylene are preferred, and polypropylene is particularly preferred.

[Regarding Blending Ratio of Polymer (a) and Polymer (b)] As the blending ratio of the polymer (a) and the polymer (b), the former is 95 to 5% by weight based on the total of both. , The latter is in the range of 5 to 95% by weight, the former is in the range of 80 to 20% by weight, and the latter is in the range of 20 to 80% by weight. If any one of the proportions is less than 5% by weight, any of the effects of the polymer (a) and the polymer (b) cannot be exhibited.

[Regarding Peroxide (c)] The peroxide (c) can be decomposed by heat to generate a free radical, and a known organic peroxide can be used. Specifically, the following can be exemplified.

Ketone peroxides such as cyclohexanone peroxide and methyl ethyl ketone peroxide,
Hydroperoxides such as 1,1,3,3-tetramethylbutyl hydroperoxide and t-hexyl hydroperoxide, dialkyl such as dicumyl peroxide and 1,3-bis (t-butylperoxyisopropyl) benzene Diacyl peroxides such as peroxides, benzoyl peroxide and lauroyl peroxide, peroxydicarbonates such as diisopropyl peroxydicarbonate and di-n-propyl peroxydicarbonate, and other peroxyesters, peroxy Ketals, etc.

The decomposition temperature is such that free radicals can be generated under the temperature conditions for obtaining the coating resin, and it depends on the conditions, but the one having a 10-hour half-life temperature in the range of 70 to 150 ° C. is preferable in terms of handling. .

The free radicals generated from these peroxides during melting can be expected to have the following effects. (1) The molecular chain of the polymer (a) and / or the polymer (b) is cleaved, the melt viscosity of the system is reduced, and the impregnation property into the glass fiber is improved. (2) Simultaneously with the reaction between the polymer (a) and the polymer (b) starting from the radical newly generated in the molecular chain by the abstraction reaction of hydrogen and the like from the polymer (a) and the polymer (b). The copolymer considered to be produced acts as a compatibilizing agent for the remaining polymer (a) and polymer (b) and facilitates mixing. (3) When a monomer (d) described later coexists, the monomer (d) reacts with a radical newly generated in the polymer (a) and / or the polymer (b) as a starting point, This is to produce a copolymer that can firmly adhere to glass fibers. In particular, when the polymer (b) is polypropylene, these effects are remarkable.

When the glass fiber is coated with the coating resin obtained by melting the components containing the polymer (a), the polymer (b) and the peroxide (c), in order to facilitate the impregnation of the glass fiber, The melt viscosity of the coating resin in the molten state is 10
It is preferably not more than 00 poise.

Various ingredients may be added to the component containing the polymer (a), the polymer (b) and the peroxide (c). For example, a surface treatment agent for glass fibers such as a silane coupling agent and a lubricant described below can be blended.

The amount of peroxide added may be determined according to the melt viscosity of the coating resin in the molten state. If the amount is too large, the reaction becomes complicated, which is not preferable in terms of workability, safety and economy. The range is preferably 0.1 to 10 parts by weight based on 100 parts by weight of the total of the polymer (a) and the polymer (b).

[Monomer (d) for improving adhesion to glass fiber] The monomer (d) improves the adhesion between the glass fiber and the vinyl chloride polymer (A), and the composition of the present invention. It can be used together with the polymer (a), the polymer (b) and the peroxide (c) to improve the physical properties of the.
That is, due to the action of free radicals generated from the peroxide (c), the monomer (d) becomes the polymer (a) and / or
Alternatively, it reacts with the polymer (b) to produce a copolymer that can firmly adhere to glass fibers.

The monomer (d) is preferably a vinyl monomer containing a functional group. As the functional group, for example,
Examples thereof include an epoxy group, a carboxyl group, a carboxylic anhydride group, an amino group, a silyl group bonded to a hydrolyzable group, an amide group, and a hydroxyl group, and an epoxy group, a carboxyl group, and a carboxylic anhydride group are particularly preferable.

Examples of the epoxy group-containing vinyl monomer include glycidyl esters such as glycidyl acrylate, glycidyl methacrylate and glycidyl itaconate, or glycidyl ethers such as vinyl glycidyl ether and allyl glycidyl ether, and especially methacrylic acid. Glycidyl and vinyl glycidyl ether are preferred.

As the carboxy group-containing vinyl monomer,
Acrylic acid, methacrylic acid, itaconic acid, maleic acid and the like can be mentioned, and methacrylic acid and maleic acid are particularly preferable.

The carboxylic acid anhydride group-containing vinyl monomer is an anhydride of a polyvalent carboxylic acid having a polymerizable unsaturated group, such as maleic anhydride, itaconic anhydride, and endic acid anhydride. Examples thereof include saturated polycarboxylic acid anhydrides, and maleic anhydride is particularly preferable.

When the amount of the monomer (d) is too large, it is not preferable because it tends to cause a secondary reaction with the polymer (a) and the polymer (b), and the crosslinking reaction results in the formation of a network structure. It becomes unmelted and the dispersibility of the glass fiber is significantly impaired, which is not preferable. Therefore, an appropriate amount is 0.1 to 20 parts by weight based on 100 parts by weight of the total of the components including the polymer (a), the polymer (b) and the peroxide (c).

[Copolymer (e)] The copolymer (e) can be used together with the polymer (a), the polymer (b) and the peroxide (c). In this case, the monomer (d) can also be used in combination. The polymer chain (X), which is a constituent of the copolymer (e), is immiscible with the vinyl chloride polymer (A) like the polymer (b), and the polymer chain (Y) is a heavy chain. Like the polymer (a), it has a property of being miscible with the vinyl chloride polymer (A), and thus is substantially a structure having the polymer (a) and the polymer (b) in one molecule. . Therefore, the copolymer which is considered to be formed by partially reacting the polymer (a) and the polymer (b) is considered to have essentially the same structure as the copolymer (e).

However, the polymer (a) and the polymer (b) are
It has completely opposite properties to the vinyl chloride polymer (A), and both are poorly miscible in nature, and when the difference in melt viscosity between the two when coating glass fibers is significantly different, It becomes increasingly difficult to mix uniformly, and the coated state of the glass fibers becomes extremely non-uniform, which may reduce the reproducibility of the characteristics.

Therefore, when the above phenomenon is remarkable due to the selected combination of the polymer (a) and the polymer (b), the copolymer (e) is used to obtain the coating resin. By this, it acts as a compatibilizing agent for the polymer (a) and the polymer (b), and uniform mixing can be carried out very easily in the initial stage of melt kneading.

In this case, the polymerized chain (X) is the polymer (b).
And the polymerization chain (Y) is a polymer (a)
It is more preferable that it has the same structure as that described above, since such an effect can be remarkably exhibited. Therefore, it is not necessary to use a large amount, and to 100 parts by weight in total of the components consisting of the polymer (a), the polymer (b) and the peroxide (c),
0.1 to 20 parts by weight is an appropriate amount.

The length of the polymerization chain (X) in the copolymer (e) is not particularly limited as long as it is immiscible with the vinyl chloride polymer (A). Similarly, the length of the polymerization chain (Y) is not particularly limited as long as it is miscible with the vinyl chloride polymer (A). However, a polymer obtained by alternately polymerizing a polymer unit that constitutes an immiscible polymer with a vinyl chloride polymer (A) and a polymer unit that constitutes a miscible polymer is preferable as the copolymer (e). Also, a polymer in which both polymerization units are randomly polymerized is not preferable as the copolymer (e).

Therefore, the copolymer (e) is preferably a block copolymer or a graft copolymer having at least one polymerization chain (X) and one polymerization chain (Y), and the polymerization chain (X) is a polymer ( A combination having the same structure as b) and the polymer chain (Y) having the same structure as the polymer (a) is more preferable. In the case of a graft copolymer, the polymerization chain (X) may be either a trunk chain or a branch chain. However, a graft copolymer in which the polymerization chain (X) is a trunk chain and the polymerization chain (Y) is a branch chain is preferable in terms of the effects of the invention, ease of production, and the like.

Polymerization chain (X) constituting the copolymer (e)
And the proportion of the polymerization chain (Y) is 95 to 5% by weight of the former,
The latter is in the range of 5% to 95% by weight, and the former is 80% by weight.
-20% by weight and the latter in the range of 20% -80% by weight are particularly preferred.

Within the above range, the effect as a compatibilizer for the polymer (a) and the polymer (b) is exhibited, which is preferable. The molecular weight of the copolymer (e) is not particularly limited, and is preferably 1,000 to 400,000 in terms of average molecular weight,
200,000 is particularly preferred.

[Specific Examples of Polymerized Chain (X)] The polymerized chain (X) is a chain containing polymerized units (m). A relatively small amount of monomer (n) or another monomer may be copolymerized with monomer (m). However, the polymer chain (X) is preferably a polymer chain formed substantially from only one or more monomers (m), and more preferably has the same structure as the polymer (b). .

Therefore, as the monomer (m), ethylene and propylene are preferable as described in the polymer (b), and propylene is particularly preferable.

[Specific Example of Polymerized Chain (Y)] The polymerized chain (Y) is a chain containing polymerized units (n), and the monomer (m) and other monomers are the monomer (n). May be copolymerized with. As the polymerization chain (Y) to be formed, a monomer (n) or a combination of the monomer (n) and the monomer (m) having substantially the same structure as the polymer (a) is used. Those selected are more preferred. Therefore, as the monomer (n), as described in the polymer (b), an acrylic acid monomer such as a vinyl chloride monomer and an alkyl acrylate monomer, and an alkyl methacrylate ester Examples include methacrylic acid-based monomers such as monomers and vinyl cyanide-based monomers.

As the monomer forming the polymerization chain (Y), a combination of acrylonitrile-styrene and methyl methacrylate are particularly preferable.

In the polymerization chain (Y) consisting of vinyl cyanide-based polymerized units and aromatic vinyl-based polymerized units, the proportion of vinyl cyanide-based polymerized units is 5 to 5 in the polymerized chain (Y) as in the case of the polymer (a). 80% by weight is preferable, and 10 to 50% by weight is particularly preferable.

The method for producing the copolymer (e) is not particularly limited, and known methods can be adopted. For example, monomer (m)
A radical-generating agent such as benzoyl peroxide or dicumyl peroxide is used in a polymer obtained by polymerizing one or more of the above, and one or more of the monomer (n) is reacted at a predetermined temperature, for example, 150 to 250 ° C. The method of making a graft copolymer is mentioned. In the polymerization reaction, a solvent such as toluene or xylene can be used as needed.

A method of directly polymerizing a block copolymer by carrying out living polymerization of at least one kind of the monomer (m) and subsequently reacting at least one kind of the monomer (n), Or
A polymer obtained by polymerizing at least one kind of the monomer (m) and a polymer obtained by polymerizing one or more kinds of the monomer (n) are separately polymerized, and a carboxyl group is added to one end of each polymer. Alternatively, there may be mentioned a method of obtaining a copolymer (e) by reacting a polymer modified by introducing an isocyanate group and a hydroxyl group or an amino group into the other, and the like.

[Regarding the Coated Glass Fiber (B)] As the glass fiber, it is preferable to use a relatively long glass fiber such as a roving shape or a chopped strand shape.
Particularly, a commercially available roving glass fiber is preferable. The glass fiber diameter is preferably 1 to 20 μm.

Further, the glass fiber is a coupling agent,
Ordinary surface treatment with a film former, a lubricant, or another surface treatment agent may be performed. For example, as the coupling agent, there is a silane compound in which a hydrolyzable group called a silane coupling agent is bonded to a silicon atom. Specific examples of the silane coupling agent include the following compounds.

Methacrylsilane compounds such as γ-methacryloxypropyltriethoxysilane and γ-methacryloxypropylmethyldiethoxysilane, epoxysilane compounds such as γ-glycidoxypropyltrimethoxysilane, and γ-aminopropyltriethoxy. Silane, N
Aminosilane compounds such as β-aminoethyl-γ-aminopropyltriethoxysilane, vinylsilane compounds such as vinyltrimethoxysilane, and chlorosilane compounds such as γ-chloropropyltrimethoxysilane.

The method of coating the glass fiber with the coating resin is not particularly limited. Usually, the components containing the polymer (a), the polymer (c) and the peroxide (c) are melt-mixed to form a coating resin in a molten state, and the glass fiber is coated with the coating resin in the molten state. Method is used. The coating resin can be cooled once, melted again, and used for coating.

Preferably, a method of impregnating and coating the glass fiber with the coating resin by continuously passing the roving glass fiber through a resin tank containing the coating resin in a molten state, and then cutting the glass fiber is used. To be At this time, the components including the polymer (a), the polymer (c) and the peroxide (c) are mixed in advance before heating, melt-kneaded at an appropriate temperature using an extruder, and then introduced into a coating resin tank. This method is preferable from the viewpoint of continuous production.

In this case, the extrusion amount of the extruder is determined by the amount of glass fiber supplied to the coating resin tank, and the temperature of the coating resin tank is such that the melt viscosity of the coating resin in the molten state is 10
It is preferably adjusted to be less than 00 poise, especially less than 500 poise. The melt viscosity of the coating resin is 1
If it exceeds 000 poise, it becomes difficult to impregnate the coating resin into the roving glass fiber, and when the coated glass fiber (B) is blended with the vinyl chloride polymer (A), the dispersion of the glass fiber becomes insufficient, The mechanical strength is not improved, and the surface appearance of the molded product is significantly impaired, which is not preferable.

The coated glass fiber (B) obtained by the above method preferably has a length of 1 to 50 mm in terms of handling, more preferably 1 to 20 mm.

The compounding amount of the coated glass fiber (B) in the composition is 10 with respect to 100 parts by weight of the vinyl chloride polymer (A).
２００200 parts by weight. If the amount is less than 10 parts by weight, the properties of the vinyl chloride resin cannot be sufficiently strengthened and improved, and
If it exceeds 0 parts by weight, the glass fiber addition efficiency is not improved so much, and conversely, the moldability is extremely lowered.

The amount of coating resin in the coated glass fiber is preferably 5% by weight or more in the coated glass fiber. If the amount of the coating resin is less than 5% by weight, the glass fibers are not completely covered, and when kneaded with the vinyl chloride polymer, the dispersibility of the glass fibers and the adhesion to the vinyl chloride polymer become insufficient. Cheap. On the other hand, if the amount of the coating resin is too large, the ratio of the coating resin to all the polymer components in the composition increases, which is disadvantageous in terms of physical properties and economy. The amount of the coating resin is preferably 60% by weight or less, and particularly preferably 40% by weight or less.

The amount of glass fiber in the composition of the present invention is preferably 5 to 100 parts by weight with respect to 100 parts by weight of the vinyl chloride polymer (A). If the amount is less than 5 parts by weight, the properties of the vinyl chloride resin cannot be satisfactorily enhanced or improved. If the amount is more than 100 parts by weight, the efficiency of glass fiber addition is not so improved, and conversely, the moldability is extremely reduced. . The amount of the resin coating the glass fibers in the composition is 10 parts by weight per 100 parts by weight of the vinyl chloride polymer.
The amount is preferably 0 parts by weight or less, particularly preferably 60 parts by weight or less.

The composition of the present invention is preferably used as a molding composition provided for molding. That is, the composition is used alone, or various compounding agents are further added to the composition for molding. Examples of the molding method of the vinyl chloride resin composition include injection molding, extrusion molding, press molding, calendering and the like which are generally applied to thermoplastic resins.

Specifically, each powder or pellet of the composition is blended using a Henschel mixer or the like,
A single-screw or twin-screw extruder or the like is melt-kneaded at 150 to 180 ° C. to obtain a molded product. In particular, it is preferably used for manufacturing a molded product by extrusion molding.

The composition of the present invention contains various known compounding agents,
That is, a stabilizer for vinyl chloride resin, an impact modifier,
Lubricants, pigments, antistatic agents, antioxidants, fillers, foaming agents, flame retardants and the like can be used as needed. The following are typical examples of these compounding agents.

Organotin heat stabilizers such as dibutyltin mercaptide, dibutyltin dilaurate and dibutyltin distearate, stabilizers of aliphatic carboxylic acid salts such as barium stearate, calcium stearate and zinc stearate, inorganic stabilizers, epoxidation Epoxy compounds such as soybean oil, stabilizers such as organic phosphates and organic phosphites, MBS
Impact modifiers such as resins and acrylic rubbers, waxes, metal soaps, lubricants of higher fatty acids such as stearic acid, phenolic antioxidants, phosphite stabilizers, antioxidants such as UV absorbers, carbon black, water Fillers such as Japanese calcium silicate, silica, calcium carbonate, talc, etc.

The total amount of these compounding agents, excluding the filler, is preferably 50 parts by weight or less with respect to 100 parts by weight of the vinyl chloride polymer (A). In addition, even if the filler is included, the total amount of these compounding agents is 1 with respect to 100 parts by weight of the vinyl chloride polymer.
It is preferably not more than 00 parts by weight.

The shape of the molded product of the composition of the present invention is not particularly limited, but it is preferably an extrusion molded product such as a plate-shaped product, a rod-shaped product or a tubular product having various sectional shapes. Typical examples of its applications include construction materials such as rain gutters, eaves, outer wall siding materials, and window frames.

[0082]

EXAMPLES The present invention will be specifically described below with reference to Examples (Examples 1 to 5) and Comparative Examples (Examples 6 to 9), but the present invention is not limited thereto.

[Preparation of Vinyl Chloride Polymer (A)] 3 Parts of Partially Saponified Polyvinyl Alcohol (Gosenol KH-20 manufactured by Nippon Gohsei Kagaku Co., Ltd.) , And 3000 parts of pure water were added to the pressure reaction type reactor, and after substitution with nitrogen gas, 1000 parts of vinyl chloride monomer was charged. After reacting at 65 ° C. for 6 hours, unreacted monomers were recovered and then dehydrated and dried to obtain 950 parts of a powdery polymer. The polymerization degree of the obtained polymer was 800. Hereinafter, this is referred to as polymer A.

[Preparation of Coated Glass Fiber (B)] The components used for the coated glass fiber are as follows. (A1) Acrylonitrile-styrene copolymer (acrylonitrile content 28% by weight, melt index (hereinafter referred to as MI) 25 g / 10 min), (b1) polypropylene (crystal melting point: 165 ° C., MI: 13 g / 10)
Min), (c1) dicumyl peroxide (10-hour half-life temperature: 117 ° C.), (d1) maleic anhydride, (e1)
Copolymer.

[Preparation of Copolymer (e)] MI is 9 g / 1
0 minutes polypropylene 60 parts, Irganox 1010
(Antioxidant manufactured by Ciba-Geigy) 0.1 part, dicumyl peroxide 1 part, acrylonitrile 10 parts and styrene 30 parts were polymerized at 170 ° C. for 2 hours under a nitrogen atmosphere. After the completion of the polymerization, the copolymer was sufficiently washed with acetone and dried to produce a copolymer.

The obtained copolymer was a graft copolymer composed of a chain consisting of propylene polymer units and a copolymer chain consisting of acrylonitrile polymer units-styrene polymer units. The chain consisting of propylene polymerized units is 70
The copolymer chain composed of acrylonitrile polymer units and styrene polymer units was 30% by weight, and the weight ratio of acrylonitrile polymer units to styrene polymer units was 28/72. Hereinafter, this is referred to as a copolymer (e1).

(1) 40 parts of the component (a1), 60 parts of the component (b1) and 2.5 parts of the component (c1) were blended using a Henschel mixer, and subsequently, using a 50 mm single screw extruder. , Cylinder temperature 250 ℃, die temperature 30
It was extruded at 0 ° C. and a rotation speed of 75 rpm, and supplied to a coating resin tank kept at 300 ° C. Components (a1), (b1),
The melt viscosity of the coating resin according to (c1) is 2.5 m in length.
When measured with a capillary having a diameter of 0.25 mm and a diameter of 0.25 mm at 300 ° C. and a shear rate of 1000 sec ⁻¹ , it was 95 poise. On the other hand, a roving-like glass fiber having a fiber diameter of 13 μm is continuously passed through a molten coating resin tank, and the coating resin is impregnated between the monofilaments.
An excess amount of the resin was removed by passing the resin component through a die having a diameter of mm, and the weight ratio of the resin component to the glass fiber was adjusted to 30/70. The obtained coated glass fiber was cut into a length of 6 mm with a rotary cutter. Hereinafter, this is referred to as a coated glass fiber (B-1).

(2) A table in which the above-mentioned components (d1) and (e1) are further added to the components (a1), (b1) and (c1) by the same production method as that used for obtaining (B-1). After the glass fiber roving was impregnated with the coating resin in the ratio shown in 1, the length was 6 mm, and the weight ratio of the resin component to the glass fiber was 30.
/ 70 coated glass fibers (B-2) to (B-5) were obtained. Table 1 shows the melt viscosity (poise) of these coating resins.

For comparison, the components (a1), (b
1), coated glass fibers (C-1) to (C-1) by the same production method as (B-1) without using any of (c1)
(C-3) was obtained. Table 1 shows the melt viscosities of these coating resins.
Shown in

Example 1 Polymer A, (B of coated glass fiber)
-1) was mixed with the amount shown in Table 2 (unit: part), 3 parts of dibutyltin mercaptide, and 0.5 part of stearic acid, and blended using a Henschel mixer. Then, using a 30 mm single screw extruder with L / D = 24 and compression ratio = 2.3, the cylinder temperature was 165 ° C. and the die temperature was 18
A flat plate having a thickness of 3 mm and a width of 30 mm was extrusion-molded at 5 ° C. and a rotation speed of 20 rpm. Extrusion moldability, glass fiber dispersibility of the obtained flat plate, surface appearance, and various physical properties were evaluated by the following methods. The results are shown in Table 3.

Extrusion moldability: Evaluation by screw load (unit: ampere), extrusion rate (unit: g / min), glass fiber dispersibility; Visually, three-stage evaluation (◯: no glass fiber bundle at all. Δ: There are some glass fiber bundles. ×: Many glass fiber bundles are evaluated. Surface appearance: Three-level evaluation by visual observation (○: No surface gloss unevenness, no roughness, no swelling. Δ: Surface gloss unevenness,
Or there is roughness and swelling. ×: Uneven surface gloss, rough, undulating. ), Tensile strength (unit: 10 ² kg / cm ² ) and tensile modulus (unit: 10 ² kg / cm ² ); JIS K7113
Bending strength (unit: 10 ² kgf / cm ² ) and bending elastic modulus (unit: 10 ² kg / cm ² ); JIS K720
3 Izod impact strength (notched) (Unit: kg cm)
/ Cm ² ); conforming to JIS K7110, heat distortion temperature (unit: ° C); conforming to JIS K7207 (load 18.5 kg / cm ² ), water resistance (unit:%); flat plate molded article in hot water at 50 ° C 7
Evaluated by the retention rate of tensile strength after immersion for a day.

[Examples 2 to 5] Polymer A, the amount (unit: part) of each of (B-2) to (B-5) of the coated glass fiber shown in Table 2, and 3 parts of dibutyltin mercaptide, and stearic acid. A flat plate molded product was prepared in the same manner as in Example 1 by mixing 0.5 parts, and various evaluations were performed. The results are shown in Table 3.

[Examples 6 to 8] Polymer A, the amounts (units: parts) of the coated glass fibers (C-1) to (C-3) shown in Table 2, and 3 parts of dibutyltin mercaptide, and stearic acid. A flat plate molded product was prepared in the same manner as in Example 1 by mixing 0.5 parts, and various evaluations were performed. The results are shown in Table 3.

[Example 9] Polymer A, roving glass fiber used for coated glass fiber was cut into 6 mm, and chopped strand glass fiber D not coated with coating resin
Were mixed in the amounts shown in Table 2 (unit: parts), 3 parts of dibutyltin mercaptide, and 0.5 part of stearic acid, and a flat plate molded article was prepared in the same manner as in Example 1, and various evaluations were performed. The results are shown in Table 3.

From Table 3, it can be seen that the tensile strength, the tensile elastic modulus, the bending strength, the bending elastic modulus, and the water resistance are all superior to those of the comparative examples. In particular, the effect of improving impact strength is high, and it exhibits extremely excellent mechanical properties. Further, it has excellent moldability and surface appearance.

[0096]

[Table 1]

[0097]

[Table 2]

[0098]

[Table 3]

[0099]

As described above, the polymer (a) which is miscible with the vinyl chloride polymer, the polymer (b) which is immiscible with the vinyl chloride polymer and which is crystalline and the peroxide (c). By blending a coated glass fiber coated with a resin such as a coating obtained by melting a component containing a) and a vinyl chloride-based polymer, the melting property of the vinyl chloride-based resin is improved by the sliding action of the polymer (b). The strength and resistance which could not be achieved by the conventional technology were significantly improved and the synergistic effect with the improvement of the dispersibility of the polymer (a) in the vinyl chloride polymer which is the matrix resin and the strengthening of the interfacial adhesion with the glass fiber. A vinyl chloride resin composition having remarkably improved impact resistance, elastic modulus, water resistance, surface appearance and moldability can be obtained.

Further, the above-mentioned components (a) to (c), a monomer (d) which further improves the adhesion to glass fiber, or a polymerization chain (X) and a chloride which are immiscible with the vinyl chloride polymer. The above polymer (a) is obtained by using a coating with a coating resin obtained by melting a component containing a copolymer (e) having a polymerization chain (Y) miscible with a vinyl polymer in the same molecule. Since the polymer (b) can be more easily mixed with the polymer (b), the glass fiber can be evenly coated with high efficiency. The composition of the present invention is extremely useful as an extrusion molding composition and the like.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Yuriko Kaita 1150, Hazawa-machi, Kanagawa-ku, Yokohama, Kanagawa Central Research Laboratory, Asahi Glass Co., Ltd. (72) Tomiya Sugiura 1150, Hazawa-machi, Kanagawa-ku, Yokohama, Asahi Glass Central Research Laboratory (72) Inventor Shigeyuki Ozawa 1150 Hazawa-machi, Kanagawa-ku, Yokohama, Kanagawa Asahi Glass Co., Ltd. Central Research Laboratory (72) Inventor Shigeharu Arai 3-28 Shin-Shiraoka, Shiraoka-cho, Minami Saitama-gun, Saitama Prefecture 5

Claims (12)

[Claims] 1. A vinyl chloride polymer (A) (100 parts by weight), a vinyl chloride polymer-miscible polymer (a), and a vinyl chloride polymer-immiscible and crystalline polymer. Coated glass fiber (B) 1 coated with a coating resin obtained by melting a component containing (b) and peroxide (c)
A composition comprising 0 to 200 parts by weight. 2. A coating resin comprising a polymer (a), a polymer (b) and a peroxide (c), and a monomer (d) for improving the adhesion to glass fiber, or a vinyl chloride resin. A resin obtained by melting a component containing a copolymer (e) having a polymer chain (X) immiscible with the polymer and a polymer chain (Y) miscible with the vinyl chloride polymer in the same molecule. The composition of claim 1, wherein: 3. The composition according to claim 1, wherein the polymer (a) is a copolymer of a vinyl cyanide monomer and an aromatic vinyl monomer or an alkyl methacrylate polymer. 4. The composition according to claim 3, wherein the polymer (a) is an acrylonitrile-styrene copolymer or polymethylmethacrylate. 5. The composition according to claim 1, wherein the crystalline melting point of the polymer (b) is 250 ° C. or lower. 6. The composition according to claim 1, wherein the polymer (b) is an olefin polymer. 7. The composition according to claim 6, wherein the polymer (b) is polypropylene. 8. The composition according to claim 1, wherein the peroxide (c) is a peroxide capable of generating a free radical under the temperature conditions for obtaining a coating resin. 9. The composition according to claim 2, wherein the monomer (d) is a vinyl monomer having a functional group selected from an epoxy group, a carboxyl group, and a carboxylic acid anhydride group. 10. The polymerization chain (X) is a polymerization chain in which an olefinic monomer is polymerized, and the polymerization chain (Y) is a copolymerization of a vinyl cyanide-based monomer and an aromatic vinyl-based monomer. The composition according to any one of claims 2 to 8, which is a polymerization chain or a polymerization chain in which an alkyl methacrylate ester-based monomer is polymerized. 11. The composition according to claim 1, wherein the coating resin has a melt viscosity of 1,000 poise or less. 12. The composition according to claim 1, wherein the coated glass fiber (B) is obtained by continuously passing the glass fiber through a coating resin in a molten state.