JP2002179906A - Abrasion resistance improver - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an abrasion resistance improver which can be mixed in various resins to provide them with improved properties in abrasion resistance, scratch resistance and slidability and with no lowered properties in impact strength and tensile strength; is excellent in workability; and is widely applicable. SOLUTION: The abrasion resistance improver comprises a polymer composition containing (I) a polyurethane block copolymer and (II) a polyurethane elastomer, wherein the polyurethane block copolymer is composed of (I-1) an addition-polymer block which consists of a block copolymer or its hydrogenated product having (A) a polymer block made from an aromatic vinyl compound unit and (B) a polymer block made from a conjugated diene compound unit or an isobutylene unit and (I-2) a polyurethane elastomer block; and (I) the polyurethane block copolymer and (II) the polyurethane elastomer have a weight ratio of 100/0-10/90.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a wear resistance improver comprising a polymer composition containing a specific polyurethane block copolymer and a polyurethane elastomer. By blending the wear resistance improving agent of the present invention with various resins, the properties of various resins such as wear resistance, scratch resistance and slidability can be improved.

[0002]

2. Description of the Related Art Resin modification technology has the advantage that development costs and development time can be greatly reduced as compared with the development of new resins based on molecular design. Research on resin modification has been actively conducted in many fields, including resins for mechanical parts. Above all, many studies have been made to improve the abrasion resistance, scratch resistance, and slidability of the resin from the viewpoint of preventing the surface of the resin molded product from being damaged and friction and abrasion. However, there are few general-purpose abrasion resistance / slidability improvers that can be used in common with other types of resins, and their improvement effects cannot be said to be sufficient (for example, see Japanese Patent Application Laid-Open No. 6-5103).
No. 17) and when mixed with other resins,
In some cases, the impact strength and the tensile properties are reduced.

[0003]

SUMMARY OF THE INVENTION An object of the present invention is to provide a resin which, when blended with various resins, significantly improves the properties of the resin such as abrasion resistance, scratch resistance and slidability, as well as impact strength and tensile strength. An object of the present invention is to provide an abrasion resistance improver which does not cause deterioration in physical properties and the like, has excellent handleability, and is versatile.

[0004]

Means for Solving the Problems The present inventors have made intensive studies to achieve the above object. As a result, when a polymer composition containing a specific polyurethane block copolymer and a polyurethane elastomer is blended with various resins, the properties such as abrasion resistance, scratch resistance, and slidability are significantly improved. And found that there was no decrease in impact strength, tensile properties, and the like, and completed the present invention.

That is, the present invention relates to an abrasion resistance improver comprising (1) a polymer composition containing a polyurethane block copolymer (I) and a polyurethane elastomer (II), and (2) a polyurethane-based improver. The block copolymer (I) comprises a block copolymer having a polymer block (A) composed of an aromatic vinyl compound unit and a polymer block (B) composed of a conjugated diene compound unit or an isobutylene unit, or a hydrogenated product thereof. (3) a polyurethane block copolymer comprising an addition polymer block (I-1) and a polyurethane elastomer block (I-2); and (3) a polyurethane block copolymer (I) and a polyurethane elastomer (II). A weight ratio of 100/0 to 10/90;耗性 is a modifier.

[0006]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below in detail. The polyurethane block copolymer (I) in the present invention is composed of the addition polymer block (I-1) and the polyurethane elastomer block (I-2) as described above. In the polyurethane-based block copolymer (I), the addition polymer block (I-1) and the polyurethane elastomer block (I-2) are connected, for example, by a chemical bond such as a urethane bond, an allohanate bond, an amide bond, and an ether bond. Are combined.

[0007] Polyurethane block copolymer (I)
Is, for example, one addition polymer block (I-1) and 1
Diblock copolymer in which two polyurethane elastomer blocks (I-2) are bonded to each other, and one polyurethane elastomer block (I- Triblock copolymer having 2) bonded thereto, and triblock having one addition polymer block (I-1) bonded to both sides of one polyurethane elastomer block (I-2). One kind of a copolymer, a multi-block copolymer or the like in which an addition polymer block (I-1) and a polyurethane elastomer block (I-2) are alternately bonded in a total of four or more. It can consist of two or more types.

[0008] Among them, the polyurethane block copolymer (I) of the present invention is excellent in the effect of improving abrasion resistance when blended with various resins, and is characterized by one addition polymer block (I-1). A diblock copolymer in which one polyurethane elastomer block (I-2) is bonded, or one addition polymer block (on each side of one polyurethane elastomer block (I-2)) It is preferably a triblock copolymer to which I-1) is bonded.

An addition polymer block (I-1) which is one component of the polyurethane block copolymer (I)
Is a block copolymer having a polymer block (A) mainly composed of an aromatic vinyl compound unit and a polymer block (B) mainly composed of a conjugated diene compound unit or isobutylene unit, or a block derived from a hydrogenated product thereof. is there.

Examples of the block structure of the polymer block (A) and the polymer block (B) constituting the addition polymer block (I-1) include the following general formulas (1) to (4).
Can be mentioned.

[0011]

_{Embedded image} (AB) _c (1) (BA) _d (2) A- (BA ′) _e (3) B- (AB ′) _f (4)

[In the above formula, A and A ′ each represent a polymer block (A), B and B ′ each represent a polymer block (B), and c, d, e and f each independently represent Indicates an integer of 1 or more. ]

The number of repetitions c, d and e in the addition polymer block (I-1) represented by the above general formulas (1) to (4)
And f can be arbitrarily determined, but are usually preferably integers in the range of 1 to 5.

The addition polymer block (I-1) is c = 1 in the above general formula (1) among the addition polymer blocks represented by the above general formulas (1) to (4). Formula: Addition diblock represented by AB or Formula: ABA ′ in which e = 1 in the above general formula (3)
More preferably, it is an addition polymerization triblock represented by

The aromatic vinyl compound used for forming the polymer block (A) constituting the addition polymer block (I-1) includes styrene, α-methylstyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, -Methylstyrene, 2,4-dimethylstyrene, vinylnaphthalene, vinylanthracene and the like. The polymer block (A) may be composed of one kind of aromatic vinyl compound unit, or may be composed of two or more kinds of aromatic vinyl compound units. Among them, the polymer block (A) is a styrene unit because the polymer to which the abrasion resistance improving agent of the present invention is blended has a high effect of improving properties such as abrasion resistance, scratch resistance and sliding property. Alternatively, it is preferably composed of α-methylstyrene units, and particularly preferably composed of styrene units.

The polymer block (B) constituting the addition polymer block (I-1) is not particularly limited as long as it is a polymer block mainly composed of a conjugated diene compound unit or an isobutylene unit. Polyisoprene block (b-1) [hereinafter sometimes referred to as "hydrogenated polyisoprene block (b-1)"],
Hydrogenated polybutadiene block (b-2) [hereinafter sometimes referred to as "hydrogenated polybutadiene block (b-2)"], hydrogenated isoprene / butadiene copolymer block (b-3) [hereinafter This is referred to as “hydrogenated polyisoprene / butadiene copolymer block (b-
3) ") and at least one polymer block selected from the group consisting of polyisobutylene blocks (b-4) because the effect of improving the wear resistance improver in the present invention is excellent. preferable.

The hydrogenated polyisoprene block (b-1), which can be a constituent block of the polymer block (B), is obtained by hydrogenating some or all of the unsaturated bonds of polyisoprene mainly composed of isoprene units to form saturated bonds. Polymer block. In the hydrogenated polyisoprene block (b-1), before hydrogenation, the unit derived from isoprene includes a 2-methyl-2-butene-1,4-diyl group [—CH ₂ —C (CH ₃ )]. ＣＨCH—CH ₂ —;
1,4-bonded isoprene unit], isopropenylethylene group [—CH ｛—C (CH ₃ ) ＣＨCH ₂ ｝ —CH
_2- ; a 3,4-bonded isoprene unit] and / or a 1-methyl-1-vinylethylene group [—C (CH ₃ )]
(CH = CH ₂ ) —CH ₂ —; 1,2-bonded isoprene unit].

Hydrogenated polybutadiene block (b-2)
Has a 1,2-bond amount of preferably 30 to 80%, more preferably
Preferably, butadiene units, which are 35 to 60%,
And some or all of the unsaturated bonds are hydrogenated
Polybutadiene block saturated with
It is. Constructs hydrogenated polybutadiene block (b-2)
Polybutadiene, preferably before hydrogenation,
30 to 80 mol%, more preferably 35 to 60 mol%
Is a vinylethylene group [-CH (CH = CH₂) -CH₂
-; 1,2-bonded butadiene unit].
Is 70 to 20 mol%, more preferably 65 to 40 mol%
Is a 2-butene-1,4-diyl group (—CH ₂-CH = C
H-CH₂-; 1,4-bonded butadiene unit).

The hydrogenated isoprene / butadiene copolymer block (b-3) is an isoprene / butadiene copolymer mainly composed of isoprene units and butadiene units, and a part of the unsaturated bond or a part thereof. All of them are copolymer blocks that have become saturated bonds by hydrogenation. In the hydrogenated isoprene / butadiene copolymer block (b-3), before hydrogenation,
The unit derived from isoprene is a 2-methyl-2-butene-1,4-diyl group, an isopropenylethylene group and / or a 1-methyl-1-vinylethylene group, and the unit derived from butadiene is vinylethylene. And / or a 2-butene-1,4-diyl group. The ratio of these groups in the isoprene / butadiene copolymer block before hydrogenation is not particularly limited. In the hydrogenated isoprene / butadiene copolymer block (b-3), the arrangement of butadiene units and isoprene units may be any of random, block, and tapered block shapes.

A hydrogenated polyisoprene block (b-1),
In the hydrogenated polybutadiene block (b-2) and the hydrogenated isoprene / butadiene copolymer block (b-3),
As described above, some or all of the carbon-carbon double bonds may be hydrogenated, but the carbon-carbon double bond in the butadiene unit and / or the isoprene unit may be partially hydrogenated. The fact that 50 mol% or more, particularly 80 mol% or more of the heavy bond is hydrogenated (that is, the degree of unsaturation is 50 mol% or less, particularly 20 mol% or less) is the wear resistance of the present invention. It is preferable because the heat resistance deterioration and weather resistance of the improver are improved.

The polyisobutylene block (b-
4) is an isobutylene unit [—C (CH ₃ ) ₂ —CH
_2- ].

In the abrasion resistance improver of the present invention, the addition polymer block (I-1) constitutes the polymer block (A).
Of the abrasion resistance improving agent of the present invention is such that the total content of the polymer block (B) is within the range of 1: 9 to 9: 1 (weight ratio). Is preferable from the viewpoint of improving the ratio, and more preferably from 2: 8 to 7: 3 (weight ratio).

The number average molecular weight of the polymer block (A) constituting the addition polymer block (I-1) is 250
It is preferably in the range of 0 to 50,000. The number average molecular weight of the polymer block (B) is 10,000 to 1
It is preferably in the range of 00000. The number average molecular weight of the addition polymer block (I-1) is 1250
It is preferably in the range of 0 to 150,000. And the polyurethane-based block copolymer (I) in the present invention may have one or more kinds of addition polymer blocks (I-1).

The polyurethane elastomer block (I-2), which is the other component of the polyurethane block copolymer (I), may be any block made of a polyurethane elastomer. Examples of the polyurethane elastomer include a polyurethane obtained by reacting a polymer diol, an organic diisocyanate, and a chain extender. The number average molecular weight of the high molecular diol used for forming such a polyurethane elastomer is in the range of 1,000 to 6,000 from the viewpoint that the effect of improving the abrasion resistance improver of the present invention is improved. Is preferred. Here, the number average molecular weight of the polymer diol referred to in the present specification is a number average molecular weight calculated based on a hydroxyl value measured according to JIS K1557.

Examples of the polymer diol which can be used for the production of the polyurethane elastomer include polyester diol, polyether diol, polyester ether diol, polycarbonate diol and polyester polycarbonate diol. And one or more of them can be formed.

The polyester diol which can be used for the production of the polyurethane elastomer is obtained by reacting at least one dicarboxylic acid component selected from aliphatic dicarboxylic acids, aromatic dicarboxylic acids and their ester-forming derivatives with a low molecular weight diol. Examples of the obtained polyester diol include polyester diols obtained by ring-opening polymerization of lactone. More specifically, the polyester diols include, for example, those having 6 to 6 carbon atoms such as glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid and dodecane diacid.
10 aliphatic dicarboxylic acids; aromatic dicarboxylic acids such as terephthalic acid, isophthalic acid and orthophthalic acid; and one or more ester-forming derivatives thereof, for example, ethylene glycol, propylene glycol, 1,4-butane C2-C2 such as diol, 1,5-pentanediol, 1,6-hexanediol, 1,9-nonanediol, 3-methyl-1,5-pentanediol, 2-methyl-1,8-octanediol Polyester diols obtained by subjecting one or more of the ten aliphatic diols to a polycondensation reaction; polycaprolactone diol; polyvalerolactone diol; and the like.

Examples of the polyether diol which can be used for producing a polyurethane elastomer include polyethylene glycol, polypropylene glycol, polytetramethylene glycol and the like. Examples of the polycarbonate diol that can be used for producing a polyurethane elastomer include aliphatic diols such as 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, and 1,8-octanediol. Examples thereof include polycarbonate diols obtained by reacting one or more species with a carbonate such as diphenyl carbonate or dialkyl carbonate or phosgene.

The type of the organic diisocyanate used for producing the polyurethane elastomer is not particularly limited, but may be an aromatic diisocyanate having a molecular weight of 500 or less,
One or more of an alicyclic diisocyanate and an aliphatic diisocyanate are preferably used. Specific examples of such organic diisocyanates include 4,4′-
Examples include diphenylmethane diisocyanate, toluene diisocyanate, p-phenylene diisocyanate, xylylene diisocyanate, naphthalene diisocyanate, hydrogenated 4,4'-diphenylmethane diisocyanate (4,4'-dicyclohexylmethane diisocyanate), isophorone diisocyanate, hexamethylene diisocyanate, and the like. Of these organic diisocyanates, 4,4'-diphenylmethane diisocyanate is preferably used.

As the chain extender that can be used for producing the polyurethane elastomer, any chain extender conventionally used for producing a polyurethane elastomer can be used, and the type thereof is not particularly limited. Among them, as the chain extender, one or more of aliphatic diols, alicyclic diols and aromatic diols are preferably used. Specific examples of preferably used chain extenders include ethylene glycol, diethylene glycol, 1,4-butanediol, 1,5-pentanediol, 2-methyl-1,3-propanediol, and 1,6.
Hexanediol, neopentyl glycol, 1,9
-Nonanediol, cyclohexanediol, 1,4-
Diols such as bis (β-hydroxyethoxy) benzene can be mentioned. Among the above, the number of carbon atoms is 2
To 6 aliphatic diols are more preferably used as a chain extender, and 1,4-butanediol is more preferably used.

In the abrasion resistance improver of the present invention, as the polyurethane elastomer constituting the polyurethane elastomer block (I-2) in the polyurethane block copolymer (I), a polymer diol, a chain extender and an organic diisocyanate are used. Polymer diol: chain extender =
1: within the range of 0.2 to 8.0 (molar ratio), and [the total number of moles of the polymer diol and the chain extender]: [the number of moles of the organic diisocyanate] = 1: 0.98 to 1. Polyurethane elastomers obtained by reacting in the range of 04 are preferably used.

The method for producing the polyurethane-based block copolymer (I) in the present invention is not particularly limited. For example, a polyurethane elastomer and an addition polymer having a functional group capable of reacting with the polyurethane elastomer at both ends or one end of the molecule. The resulting mixture is kneaded under melting conditions, and a polyurethane-based block copolymer (I) having an addition polymer block (I-1) and a polyurethane elastomer block (I-2) is extracted from the obtained polyurethane-based reaction product. It can be obtained by collecting.

In the above, as the addition polymer having a functional group capable of reacting with the polyurethane elastomer used for producing the polyurethane block copolymer (I), the above-mentioned addition polymer block (I-1) has a functional group. An addition polymer having a bonded structure is preferably used. The functional group in that case is not particularly limited as long as it is a functional group capable of reacting with the polyurethane elastomer. Examples thereof include a hydroxyl group, an amino group, an isocyanate group, an ester group, an amide group, a carboxyl group, an epoxy group, a thiol group, and a thioester. And the like. Among them, an amino group, a hydroxyl group, and an isocyanate group are particularly preferable.

In the addition polymer having a functional group capable of reacting with the polyurethane elastomer, the functional group may be located in the middle of the molecular main chain or the side chain of the addition polymer or at any of the molecular terminals. In a preferred block form of the polyurethane block copolymer (I) of the present invention, one addition polymer block (I-1) and one polyurethane elastomer block (I-2) are bonded in a chain. In order to form a di- or tri-block type block copolymer, the addition polymer preferably has a functional group at one or both terminals, particularly the addition polymer block (I-1). ) Is preferably bonded to the end of the polymer block (A).

In the present invention, the melt kneading of the above-mentioned addition polymer having a functional group and the polyurethane elastomer for obtaining the polyurethane block copolymer (I) is carried out by a single-screw extruder, a twin-screw extruder, a kneader or a Banbury. It can be performed using a melt kneading device such as a mixer. The conditions for melt-kneading can be appropriately selected according to the type of the addition polymer or polyurethane elastomer to be used, the type of equipment, and the like.
It is good to do for about a minute.

The polyurethane-based block copolymer (I) may be prepared, for example, by reacting a polymer diol, an organic diisocyanate and a chain extender in an extruder to produce a polyurethane elastomer. A polyurethane-based reaction containing a polyurethane-based block copolymer (I) by adding an addition polymer having a functional group capable of reacting with the above-mentioned polyurethane elastomer to the reaction system at the beginning of or during the reaction of It can also be obtained by forming a product and extracting and recovering the polyurethane-based block copolymer (I) from the polyurethane-based reaction product.

The above-mentioned polyurethane-based reaction product obtained by reacting a polyurethane elastomer with an addition polymer having a functional group is a polyurethane elastomer, a polyurethane-based block copolymer (I), and an addition polymer. It is a mixture mainly composed of those. Therefore, the amount of the polyurethane-based block copolymer (I), the amount of the unreacted polyurethane elastomer, and the amount of the unreacted addition polymer contained in the polyurethane-based reaction product obtained above were calculated, and the abrasion resistance was calculated. While adjusting the contents of the polyurethane-based block copolymer (I) and the polyurethane elastomer in the improver so as to be within the preferred ranges, the polyurethane-based reaction product is used as it is [ie, the polyurethane-based reaction product is separated from the polyurethane-based block. The copolymer (I) is not recovered and remains in the form of a reaction product] and may be used in the wear resistance improver of the present invention.

The polyurethane elastomer (II) in the present invention is not particularly limited, and for example, the same type of polyurethane elastomer used for producing the above-mentioned polyurethane block copolymer (I) can be used.

The method for producing the polyurethane elastomer (II) is not particularly limited, and a prepolymer method, a one-shot method and a known urethanation reaction using the above-mentioned polymer diol, organic diisocyanate and chain extender. It may be manufactured by any of the methods. Among them, it is preferable to carry out melt polymerization substantially in the absence of a solvent, and it is particularly preferable to carry out production by continuous melt polymerization using a multi-screw extruder.

Further, a polyurethane elastomer (II)
Has a hardness (JIS A hardness; measured at 25 ° C.) of 55 to 9
The value of 0 is preferred from the viewpoint that the effect of improving the wear resistance improving agent of the present invention becomes good.

In the wear resistance improving agent of the present invention, the weight ratio of the polyurethane block copolymer (I) to the polyurethane elastomer (II) is 100/0 to 10/90.
From 100/0 to 20/8 from the point that the effect of improving wear resistance when blended with another resin is excellent.
The range of 0 is more preferable, and the range of 100/0 to 30/70 is further preferable.

The method for producing the abrasion resistance improver of the present invention is not particularly limited, and any method can be used as long as it can uniformly mix the above-mentioned polyurethane block copolymer (I) and polyurethane elastomer (II). And usually a melt-kneading method is used. Melt kneading can be performed using, for example, a melt kneading apparatus such as a single screw extruder, a twin screw extruder, a kneader, a roller, and a Banbury mixer, and is usually at a temperature of about 150 to 300 ° C. for about 30 seconds to 5 minutes.
By melt-kneading for about a minute, a polymer composition constituting the wear resistance improver of the present invention can be obtained.

The abrasion resistance improver of the present invention has excellent compatibility with various resins, and when blended with various resins, does not cause a decrease in fluidity or the generation of a gel, resulting in good handling. The properties of various resins, such as wear resistance, scratch resistance, and slidability, can be improved by their properties and moldability. Therefore, the abrasion resistance improver of the present invention is extremely effective as a versatile resin modifier for improving the properties of various resins such as abrasion resistance, scratch resistance and slidability. Can be used for

The abrasion resistance improving agent of the present invention may optionally contain various additives (for example, a reinforcing agent such as glass fiber and its surface treating agent, an antioxidant, a thermal decomposition inhibitor, an ultraviolet absorber, talc, etc.). Crystallization nucleating agent, crystallization accelerator, coloring agent,
One or more of flame retardants, fillers, release agents, plasticizers, antistatic agents, hydrolysis inhibitors, adhesion aids, adhesives, etc.) and one or more of other resins. It may be. The abrasion resistance improver of the present invention may contain one or more of the above-mentioned various additives and other resins, if necessary, to produce various molded products and other uses (for example, for fiber). Manufacturing) can be used effectively.

The type of the resin to be modified to which the antiwear agent of the present invention is blended is not particularly limited, and is effective for modifying the physical properties of both thermoplastic polymers and thermosetting polymers. However, among them, it is suitable as a modifier for a thermoplastic polymer. The abrasion resistance improver of the present invention may be used by being compounded in one kind of resin to be modified, or may be used by being compounded in a resin composition composed of two or more kinds of resins.

Examples of the resin to be modified by the abrasion resistance improver of the present invention include olefin polymers, styrene polymers, styrene-diene copolymers, and hydrogenated styrene-diene copolymers. Examples of the additive include a polyacetal polymer, a polyphenylene ether polymer, a polyamide polymer, a polyester polymer, a polyester polymer, a polycarbonate polymer, and / or an acrylic polymer.

The amount of the antiwear agent of the present invention to be added to the resin to be modified is not particularly limited, and can be adjusted according to the type, physical properties, application and the like of the resin to be modified. In general, when the abrasion resistance improver of the present invention is blended in a proportion of 1 to 50 parts by weight, preferably 3 to 30 parts by weight with respect to 100 parts by weight of the resin to be modified, the modifying effect is exhibited.

The method of blending the antiwear agent of the present invention with the resin to be modified is not particularly limited, and may be an appropriate method depending on the type and properties of the resin to be modified. For example,
When the resin to be modified is a thermoplastic polymer, one or more of the resins to be modified are added with the abrasion resistance improver of the present invention, and a suitable melt kneading apparatus such as a single screw extruder is used. Properties such as abrasion resistance, scratch resistance, and slidability are improved by the abrasion resistance improver of the present invention by using a kneader such as an extruder, twin-screw extruder, kneader, or Banbury mixer. Thus, a modified resin composition to be modified can be obtained. Further, the method of molding the modified resin composition containing the wear resistance improving agent of the present invention is not limited at all, and depending on the physical properties of each resin composition, for example, injection molding, extrusion molding, It can be molded by any molding method such as press molding, blow molding, calender molding, cast molding and the like.
Further, the use of the modified resin composition is not limited to the production of molded articles, depending on the properties and uses of each resin to be modified, in addition to molded articles, for example, paints, adhesives, sealants, It can be used for fibers and other uses.

[0048]

EXAMPLES The present invention will be specifically described below with reference to examples and the like, but the present invention is not limited thereto. In the following test examples and comparative test examples, preparation of test pieces, tensile strength at break, tensile elongation at break, flexural modulus, notched IZOD
The measurement of the impact value, the Taber abrasion amount and the limit PV value was performed as follows.

Preparation of Test Specimens Using the resin composition pellets obtained in the Test Examples or Comparative Test Examples, using an 80-ton injection molding machine manufactured by Nissei Plastics Co., Ltd., Test Examples 1 to 6 and Comparative Examples Test Examples 1-4
In case of, cylinder temperature 220 ° C and mold temperature 4
Injection molding was carried out at 0 ° C. to obtain a test piece for measuring tensile strength at break and elongation at break (No. 3 dumbbell) and a test piece for measuring the amount of Taber abrasion (size: length × width × thickness = 2).
00 mm x 200 mm x 2 mm). In the case of Test Examples 7 to 10 and Comparative Test Example 5, injection molding was performed under the conditions of a cylinder temperature of 200 ° C. and a mold temperature of 40 ° C., and a test piece for measuring tensile breaking strength and tensile breaking elongation ( No. 1 dumbbell), a test piece for measuring flexural modulus (dimensions: length × thickness × width = 128 mm × 12.7 mm × 6.
4 mm), a notched test piece for measuring the IZOD impact value (dimensions: length x thickness x width = 64 mm x 12.7 mm x
3.2 mm) and a test piece for measuring the limit PV value (dimensions: length × width × thickness = 80 mm × 80 mm × 3 mm).

Measurement of Tensile Rupture Strength and Tensile Rupture Elongation Using the test pieces prepared as described above, using Autograph (manufactured by Shimadzu Corporation), Test Examples 1 to 6 and Comparative Test Examples 1 to 4 In this case, the tensile strength at break and the tensile elongation at break were measured at 500 mm / min according to JIS-K6301. Further, in the case of Test Examples 7 to 10 and Comparative Test Example 5, 5 in accordance with JIS-K7113
The tensile strength at break and tensile elongation at break were measured under the condition of mm / min.

Measurement of Flexural Modulus The test specimen prepared above was used to measure flexural modulus using an autograph (manufactured by Shimadzu Corporation) according to JIS-K7203.

Measurement of Notched IZOD Impact Value Using the test piece prepared above, a notched Izod with a notched at 23 ° C. using an Izod impact tester (manufactured by Toyo Seiki Seisaku-sho, Ltd.) in accordance with JIS-K7110. The impact value was measured.

Measurement of Taber Abrasion Abrasion after 1000 rotations with a load of 1 kg using the test piece prepared above and a Taber abrasion tester (manufactured by Toyo Seiki Seisaku-sho, Ltd.) according to JIS-K6264. The amount was measured.

Measurement of Limit PV Value Using the test piece prepared above, a surface pressure of 5 kg / cm ² was measured using a friction and wear tester (manufactured by A & D Corporation) in accordance with JIS-K7218. , Sliding speed 50
Under conditions of ~ 200 cm / sec, the limit PV value was measured against steel material S45C (sandpaper finish) as a mating material.

Next, the samples used in the examples are shown below. SEEPS-OH having a hydroxyl group at one end, polystyrene block (number average molecular weight 6000) / 1 hydrogenated copolymer block of 1,3-butadiene and isoprene (number average molecular weight 28,000)
/ Polystyrene block (number average molecular weight 6000) triblock copolymer (hydroxyl content in triblock copolymer = 0.8 / molecule; styrene unit content in block copolymer before hydrogenation = 30 weight) %; 1,3-butadiene / isoprene molar ratio before hydrogenation = 1/1; 1,4 in 1,3-butadiene unit in a copolymer block of 1,3-butadiene and isoprene before hydrogenation. -Amount of binding = 95%, 1,2- amount of binding =
5%; 1,4-bond amount in isoprene units = 95%,
3,4-bond amount = 5%; unsaturation degree based on hydrogenated 1,3-butadiene / isoprene copolymer block = 5
%; Number average molecular weight of the entire triblock copolymer = 400
00).

[0056] polyurethane elastomer produced by Kuraray Co., Ltd. "Kuramilon 8165"

<Example 1> (1) Pre-dried polyurethane elastomer 100
Parts by weight and 100 parts by weight of SEEPS-OH, and then premixed, and then a twin-screw extruder (“B
T-30 ”), melt-kneaded under the conditions of a cylinder temperature of 220 ° C. and a screw rotation speed of 150 rpm, extruded and cut to produce pellets of a polyurethane reaction product. (2) Unreacted polyurethane was extracted and removed from the pellets of the polyurethane reaction product obtained in the above (1) using dimethylformamide, and then unreacted SEEPS-OH was extracted and removed using cyclohexane and remained. By drying the solid, a polyurethane-based block copolymer (I) comprising a polyurethane block and a block derived from SEEPS-OH was obtained, and this was used alone as an abrasion resistance improver (hereinafter referred to as abrasion resistance improvement). Used in later-described test examples and comparative test examples.

Example 2 (1) Pre-dried polyurethane elastomer 100
Parts by weight and 100 parts by weight of SEEPS-OH, and then premixed, and then a twin-screw extruder (“B
T-30 ”), melt-kneaded under the conditions of a cylinder temperature of 220 ° C. and a screw rotation speed of 150 rpm, extruded and cut to produce pellets of a polyurethane reaction product. (2) Unreacted polyurethane was extracted and removed from the pellets of the polyurethane reaction product obtained in the above (1) using dimethylformamide, and then unreacted SEEPS-OH was extracted and removed using cyclohexane and remained. The solid was dried to obtain a polyurethane block copolymer (I) comprising a polyurethane block and a block derived from SEEPS-OH. (3) Subsequently, after premixing 70 parts by weight of the polyurethane block copolymer (I) and 30 parts by weight of the preliminarily dried polyurethane elastomer, a twin-screw extruder (“BT-30” manufactured by Plastics Industry Laboratory) ), The cylinder temperature is 220 ° C. and the screw speed is 1
Melted and kneaded under the condition of 50 rpm, extruded, cut,
A polymer composition comprising a polyurethane block copolymer (I) and a polyurethane elastomer was obtained. This polymer composition was used as a wear resistance improver (hereinafter, sometimes referred to as a wear resistance improver) in test examples and comparative test examples described later.

<Test Examples 1-4> (1) Triblock copolymer of styrene-hydrogenated isoprene-styrene ("Septon 2" manufactured by Kuraray Co., Ltd.)
002 ") [this may be abbreviated as SEPS] with respect to the abrasion resistance improver of the present invention obtained in the above Example 1 or Example 2 at a ratio shown in Table 1 below. After that, the twin screw extruder (“BT” manufactured by Plastics Industrial Research Institute)
-30 "), melt-kneaded under the condition of a cylinder temperature of 220 ° C., extruded, cooled and cut to produce resin composition pellets. (2) A test piece was prepared from the pellet obtained in (1) by the method described above, and its tensile strength at break, tensile elongation at break, and Taber abrasion were measured by the above method. As shown in FIG.

<Test Examples 5 and 6> (1) Wear resistance of the present invention obtained in Example 1 or Example 2 above against polyolefin ("Engage 8200" manufactured by DuPont Dow Elastomer Co., Ltd.) After premixing the property improver at the ratio shown in Table 1 below, the mixture was supplied to a twin-screw extruder ("BT-30" manufactured by Plastics Industry Laboratory), melt-kneaded under the condition of a cylinder temperature of 220 ° C, and extruded. Then, the mixture was cooled and cut to produce pellets of the resin composition. (2) A test piece was prepared from the pellet obtained in (1) by the method described above, and its tensile strength at break, tensile elongation at break, and Taber abrasion were measured by the above method. As shown in FIG.

<Comparative Test Examples 1 and 3> (1) Triblock copolymer of styrene-hydrogenated isoprene-styrene ("Septon 2" manufactured by Kuraray Co., Ltd.)
002 ") A test piece was prepared by the above-mentioned method using a single pellet or a single pellet of polyolefin (" Engage 8200 "manufactured by DuPont Dow Elastomer Co., Ltd.), and its tensile strength at break, tensile elongation at break and Taber When the amount of wear was measured by the above-described method, it was as shown in Table 1 below.

<Comparative Test Example 2> (1) Triblock copolymer composed of styrene-hydrogenated isoprene-styrene ("Septon 2" manufactured by Kuraray Co., Ltd.)
002)), p-phenylene terephthalamide particles ("Twaron T5011" manufactured by Nippon Aramid Co., Ltd.) (hereinafter, may be abbreviated as aramid particles) as an abrasion resistance improver in a ratio shown in Table 1 below. After pre-mixing, the mixture is supplied to a twin-screw extruder ("BT-30" manufactured by Plastics Industry Research Institute), melt-kneaded under the condition of a cylinder temperature of 220 ° C, extruded, cooled, cut, and pelletized of a resin composition. Was manufactured respectively. (2) A test piece was prepared from the pellet obtained in (1) by the method described above, and its tensile strength at break, tensile elongation at break, and Taber abrasion were measured by the above method. As shown in FIG.

<Comparative Test Example 4> (1) Particles of p-phenylene terephthalamide (manufactured by Nippon Aramid Co., Ltd.) as a wear resistance improver for a polyolefin ("Engage 8200" manufactured by Dupont Dow Elastomer Co., Ltd.) Twaron T5011 ") was premixed at the ratio shown in Table 1 below, and then supplied to a twin-screw extruder (" BT-30 "manufactured by Plastics Industrial Research Institute) and melt-kneaded at a cylinder temperature of 220 ° C. The resin composition was extruded, cooled, and cut to produce resin composition pellets. (2) A test piece was prepared from the pellet obtained in (1) by the method described above, and its tensile strength at break, tensile elongation at break, and Taber abrasion were measured by the above method. As shown in FIG.

[0064]

[Table 1]

<Test Examples 7 to 10> (1) Wear resistance of the present invention obtained in Example 1 or Example 2 above against polyacetal (“Duracon M90-44” manufactured by Polyplastics Co., Ltd.) After pre-mixing the property improver at the ratio shown in Table 2 below, the mixture was supplied to a twin-screw extruder ("BT-30" manufactured by Plastics Industry Research Institute), melt-kneaded at a cylinder temperature of 200 ° C, and extruded. Then, the mixture was cooled and cut to produce pellets of the resin composition. (2) Using the pellets obtained in the above (1), a test piece was prepared by the method described above, and its tensile strength at break, tensile elongation at break, flexural modulus, notched IZOD impact value and critical PV value were determined as described above. Table 2 below
Was as shown in FIG.

<Comparative Test Example 5> (1) A test piece was prepared by the above-mentioned method using a pellet of polyacetal ("Duracon M90-44" manufactured by Polyplastics Co., Ltd.) alone.
The tensile elongation at break, the flexural modulus, the notched IZOD impact value, and the critical PV value were measured by the methods described above, and were as shown in Table 2 below.

[0067]

[Table 2]

From the comparison between the results of Test Examples 1 to 6 in Table 1 above and the results of Comparative Test Examples 1 and 3, the resin compositions of Test Examples 1 to 6 containing the wear resistance improving agent of the present invention were added. Indicates that the abrasion resistance is significantly improved as compared with Comparative Test Example 1 and Comparative Test Example 3, which do not contain the wear resistance improving agent of the present invention. Also, from the comparison of the results of Test Examples 1 to 6 and Comparative Test Examples 2 and 4 in Table 1 above, the resin compositions of Test Examples 1 to 6 in which the wear resistance improver of the present invention was blended, Compared with Comparative Test Example 2 and Comparative Test Example 4 in which aramid particles were blended as an abrasion resistance improver, the abrasion resistance was remarkably excellent, and it was found that there was no decrease in tensile breaking strength and tensile breaking elongation. Further, from the comparison of the results of Test Examples 7 to 10 in Table 2 and Comparative Test Example 5, Test Example 7 in which the wear resistance improving agent of the present invention was blended.
It can be seen that the resin compositions of Nos. 10 to 10 have significantly improved abrasion resistance as compared with Comparative Test Example 5 in which the abrasion resistance improving agent of the present invention was not blended.

[0069]

The abrasion resistance improver of the present invention is extremely effective as a versatile resin modifier which can be commonly used for various polymers. By blending with various resins, properties such as wear resistance, scratch resistance and slidability of the resins can be improved. And the abrasion resistance improver of the present invention is excellent in handleability, and when mixed in the resin to be modified, does not cause problems such as a decrease in fluidity of the resin composition and occurrence of gelation, A modified polymer composition having improved quality can be obtained. The wear resistance improving agent of the present invention is an olefin polymer, a styrene polymer, a styrene-diene copolymer or a hydrogenated product thereof, a polyacetal polymer, a polyphenylene ether polymer, a polyamide polymer,
It can be used particularly effectively as a modifier for polyester-based polymers, polyester-based polymers, polycarbonate-based polymers and / or acrylic-based polymers.

 ────────────────────────────────────────────────── ─── Continuing from the front page (72) Inventor Kazunari Ishiura 1-112-39 Umeda, Kita-ku, Osaka-shi, Osaka F-term in Kuraray Co., Ltd. CK02X CK03X CK04X CL00Y FD20W FD20X GT00

Claims (3)

[Claims] 1. An abrasion resistance improver comprising a polymer composition containing (1) a polyurethane block copolymer (I) and a polyurethane elastomer (II), and (2) a polyurethane block copolymer. (I) a block copolymer having a polymer block (A) composed of an aromatic vinyl compound unit and a polymer block (B) composed of a conjugated diene compound unit or isobutylene unit or an addition polymer composed of a hydrogenated product thereof Block (I
-1) and a polyurethane elastomer block (I
(3) a weight ratio of the polyurethane block copolymer (I) to the polyurethane elastomer (II) is 100/0.
Abrasion resistance improver comprising a polymer composition. 2. The polymer block (B) comprises a hydrogenated polyisoprene block (b-1), a hydrogenated polybutadiene block (b-2), and a hydrogenated isoprene / butadiene copolymer block (b). The abrasion resistance improver according to claim 1, which is at least one polymer block selected from the group consisting of b-3) and a polyisobutylene block (b-4). 3. An olefin polymer, a styrene polymer, a styrene-diene copolymer, a hydrogenated product of a styrene-diene copolymer, a polyacetal polymer, a polyphenylene ether polymer, a polyamide polymer, and a polyester. The wear resistance improver according to claim 1 or 2, which is a modifier for a system polymer, a polyester polymer, a polycarbonate polymer, and / or an acrylic polymer.