JP3489613B2 - Modifier for polyolefin resin and polyolefin resin composition - Google Patents

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a modifier for polyolefin resins and a polyolefin resin composition. The polyolefin-based resin composition of the present invention has good secondary processability such as painting, printing, and adhesion, and its molded article has good physical and chemical properties, so household products, various containers, various parts It can be used in a wide range of fields.

[0002]

2. Description of the Related Art Conventionally, polyolefin resins have been used in large amounts in a wide range of fields such as household products, various containers, and various parts because of their good physical and chemical properties.
However, the polyolefin resin is chemically inactive because it has neither polar group nor functional group in the molecule, and also has poor solubility in solvents, and thus has poor adhesion for coating, printing, adhesion, etc. It was difficult to perform secondary processing on the surface of the molded product. Therefore, various surface treatment methods and various resin compositions containing additives have been proposed in order to easily perform secondary processing on the surface of the polyolefin-based molded product.

Examples of the surface treatment method for polyolefin molded articles include flame treatment, corona discharge treatment, and oxidation treatment with a chromic acid-sulfuric acid mixture. However, flame treatment, corona discharge treatment and the like have problems that special equipment is required and the shape of the molded product is restricted. In addition, the oxidation treatment with a chromic acid-sulfuric acid mixed solution has problems that dangerous chemicals are used and the operation is complicated, and the applicable coating materials are also limited. In addition, there is a problem that the treatment effect becomes weaker with the lapse of time in these methods of surface treatment.

Inorganic or organic fillers have been proposed as the additives to be added to the resin composition, and the resin composition containing such an additive can be used in a selected range such as a paint which can be secondarily processed. There is a problem that is narrow. On the other hand, although a method of using an organic compound as an additive has been studied,
No improvement in wettability was observed, and the effect of improving the adhesion of the coating film was weak, which was not satisfactory.

[0005]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a polyolefin resin composition having good secondary processability such as painting, printing and adhesion.

[0006]

Means for Solving the Problems In order to solve the above problems, the inventors of the present invention have conducted extensive studies on various additives to be added to a polyolefin resin, and as a result, the polyolefin resin contains a specific hydroxyl group. The present invention has been completed by finding the fact that the secondary processability of the obtained resin composition is improved by containing the petroleum resin.

That is, the present invention has a hydroxyl value of 10 to 25.
A polyolefin-based resin modifier containing an alcohol-modified petroleum resin of 0 or a hydride thereof; and a polyolefin-based resin composition containing a polyolefin resin (B) and the modifier (A). Regarding things.

[0008]

BEST MODE FOR CARRYING OUT THE INVENTION For the polyolefin resin of the present invention
The hydroxyl value used as the modifier (A) is from 10 to 25.
Alcohol-modified petroleum resin, which is 0, contains petroleum fraction as the main component.
And having an alcoholic hydroxyl group in the resin
Can be used without particular limitation. Also, alcoholic hydroxyl groups
The method for producing a petroleum resin containing is also not particularly limited. Such water
Petroleum resins containing acid groups are, for example, the thermal decomposition of naphtha.
The petroleum fraction (C5 fraction, C9 fraction) obtained by
When producing a petroleum resin by combining
Obtained by modifying petroleum resin with organic compounds
It

[0009]

As the C5 fraction among the petroleum fractions,
For example, dicyclopentadiene and the like can be mentioned. Further, as C9 fraction, styrene, vinyltoluene, α
-Methylstyrene, indene and the like can be mentioned.

Further, as a hydroxyl group-containing compound capable of introducing an alcoholic hydroxyl group into a petroleum resin, an alcohol compound
I can give you something. Specific examples of alcohol compounds include:
Examples thereof include alcohol compounds having a double bond such as allyl alcohol . These hydroxyl group-containing compounds may be used alone or in combination of two or more.

Further, a petroleum resin containing an alcoholic hydroxyl group (hereinafter, a petroleum resin containing a hydroxyl group or a hydroxyl group
The term "containing petroleum resin" refers to a method in which a (meth) acrylic acid alkyl ester or the like is thermally polymerized with a petroleum fraction to introduce an ester group into the petroleum resin, and then the ester group is reduced. Remaining or introduced, then the method of hydrating the double bond, after thermally polymerizing vinyl carboxylate such as vinyl acetate with petroleum fraction to introduce an acyloxy group into the petroleum resin, then hydrolyze the acyloxy group It can also be manufactured by a method such as

In the present invention, in particular, an alcohol-modified dicyclopentadiene-based petroleum resin obtained by copolymerizing dicyclopentadiene and allyl alcohol or the like by thermal polymerization or the like (for example, JP-A-50-132060) is used. It is preferable that it is easy to control the hydroxyl value that contributes to the adhesiveness .

The hydroxyl group content of the hydroxyl group-containing petroleum resin is not particularly limited, but the alcohol-modified petroleum resin preferably has a hydroxyl value of about 10 to 250. The smaller the hydroxyl value, the smaller the effect of modifying the adhesiveness and the like. Therefore, the hydroxyl value is more preferably 50 or more. Further, when the hydroxyl value becomes large, the molecular weight becomes small and the workability tends to deteriorate, so that the hydroxyl value becomes 2
It is more preferably 30 or less. In order to adjust the hydroxyl value of the alcohol-modified dicyclopentadiene-based petroleum resin within the above range, usually about 10 to 200 parts by weight of an alcohol compound is copolymerized with 100 parts by weight of dicyclopentadiene.

[0015]

The softening point of the hydroxyl group-containing petroleum resin of the present invention thus obtained is preferably about 70 to 200 ° C. Since the rigidity of the obtained polyolefin resin composition can be maintained high, the lower limit of the softening point is 90 ° C., and further 12
More preferably, the temperature is 0 ° C. On the other hand, from the viewpoint of the secondary molding processability of the obtained polyolefin resin composition, the upper limit of the softening point is more preferably 180 ° C. The glass transition temperature (Tg) is preferably about 40 to 130 ° C,
More preferably, the lower limit is 70 ° C and the upper limit is 110 ° C.

The average molecular weight of the hydroxyl group-containing petroleum resin is not particularly limited, but generally, the number average molecular weight is 100 to 200.
About 0 is preferable. When the number average molecular weight is small, the softening point is low and the workability tends to be poor. Therefore, the number average molecular weight is more preferably 350 or more. on the other hand,
When the number average molecular weight is high, the softening point is high and kneading tends to be difficult. Therefore, the number average molecular weight is 1
It is more preferably 500 or less.

For the polyolefin resin of the present invention
Is a modifier may be used hydrides hydrogenating the alcohol-modified petroleum resins. The hydride has a hydrogenation rate of 5 to 100%, is a resin excellent in color tone, and usually has a color tone Gardner of 3 or less. Incidentally, the softening point of the hydride, the hydroxyl value, the constant such as the average molecular weight, it is preferable to use the same as the unhydride,
Since the constant depends on the hydrogenation conditions, the hydrogenation conditions are appropriately set to adjust the constants such as the hydroxyl value.

The hydrogenation conditions are such that the hydrogenation pressure is 10 to 300.
kg / cm ² (the lower limit is preferably 30 kg / cm ² , the upper limit is preferably 250 kg / cm ² ), and the reaction temperature is approximately 100 to 400 ° C. (the lower limit is 140 ° C. and the upper limit is preferably 350 ° C.). . Hydrogenation pressure is 1
When the reaction temperature is less than 0 kg / cm ² or the reaction temperature is 140
If the temperature is lower than 0 ° C, the hydrogenation reaction is difficult to proceed unless the reaction solvent is added. Also, the reaction temperature is 300
When the temperature is higher than 0 ° C, the hydrogenolysis reaction of the resin becomes significant, which is not preferable in any case. The reaction time for hydrogenation is usually about 10 minutes to 7 hours, preferably 20 minutes to
7 hours. It should be noted that the above description does not exclude hydrogenation under conditions outside the above range, and for example, hydrogenation is possible if a catalyst that can react even at a hydrogenation pressure of 10 kg / cm ² or less is used. Is possible.

As the hydrogenation catalyst, various kinds of metals such as metals such as nickel, palladium, platinum, cobalt, rhodium, ruthenium and rhenium or metal compounds such as oxides and sulfides thereof can be used. Such a hydrogenation catalyst may be used by supporting it on a carrier such as alumina, silica (diatomaceous earth), carbon, titania, etc., which is porous and has a large surface area. Among these catalysts, nickel-diatomaceous earth catalysts are preferable in terms of hydrogenation efficiency of unsaturated bonds and cost.
The amount of the catalyst used is usually 0.01 to 5 with respect to the raw material resin.
It is about% by weight.

The hydrogenation reaction is carried out in a state where the raw material resin is melted or dissolved in a solvent. Any solvent may be used as long as it is inert to the reaction and easily dissolves the raw materials and products. For example, cyclohexane, n-hexane, n-heptane, decalin, isopropyl alcohol, tetrahydrofuran and the like can be used alone or in combination of two or more. The amount of the solvent used is not particularly limited, but the solid content is usually 10% by weight or more, preferably 10 to 70% by weight based on the raw material resin.

Regarding the amount of the catalyst used and the reaction time, the case where the batch system is adopted as the reaction system has been described, but the flow system (fixed bed system, fluidized bed system, etc.) may be adopted as the reaction system. it can.

The polyolefin resin composition of the present invention, the polyolefin resin (B), is obtained by adding a polyolefin resin modifier for containing a petroleum resin and containing not (A) a hydroxyl group, the modified The quality improver (A) improves the secondary processability of the polyolefin resin (B).

The polyolefin resin (B) used in the present invention is a homopolymer of an α-olefin having 2 to 6 carbon atoms such as ethylene, propylene, butene, methylpentene, and any two kinds of the α-olefin. And the like. Specifically, examples thereof include polyethylene, polypropylene, polybutene, polymethylpentene, and a copolymer of ethylene and propylene. The polyolefin resin (B) of the present invention
Can be obtained by a generally known method.

The number average molecular weight of the polyolefin resin (B) is not particularly limited, but is usually 100,000.
~ 800,000 is preferable, and the lower limit is 1500.
00, and the upper limit is more preferably 500000.

The compounding amount of the modifier (A) is usually 0.1 to 100 parts by weight of the polyolefin resin (B).
50 parts by weight is preferable, the lower limit is 0.5 part by weight, and the upper limit is 30 parts by weight.

The method of adding the modifier to the polyolefin resin (B) is not particularly limited. For example, in addition to the method of melting and mixing the polyolefin resin (B) and the modifier (A), the polyolefin resin (B) and the modifier (A) are mixed and kneaded by an extruder or a molding machine. You can also do it.

The polyolefin resin composition of the present invention has a surface tension of 33 to 39 mN when formed into a film.
/ M, good wettability and excellent secondary workability.

Further, in the polyolefin resin composition of the present invention, various known additives other than the above-mentioned components, such as stearic acid, behenic acid, their metal salts (calcium, magnesium, zinc, etc.), ethylenebisstearin. An acid amide or the like can also be added. Further, a nucleating agent, a pigment, a coloring agent, an antioxidant, an antistatic agent, a flame retardant, etc. can be added.

The polyolefin resin composition of the present invention can be used in various forms in a wide range of fields such as household products, various containers and various parts. For example, films used for food packaging, textile packaging, sundries packaging, tapes, interiors of buildings, surface makeup of fittings, vehicle interiors, sheets used for various containers, interiors and exteriors of various parts and household items, etc. Injection-molded products used, interior materials such as automobiles and home appliances
It can be used in various forms such as foams used as housing materials for OA equipment, packaging materials and the like.

[0031]

EFFECT OF THE INVENTION The polyolefin resin composition of the present invention has good wettability, excellent printability, paint adhesion, adhesiveness, and the like, and is easily subjected to secondary processing such as painting, printing, and adhesion.

[0032]

EXAMPLES The present invention will be described in more detail with reference to Examples and Comparative Examples, but the present invention is not limited thereto. In addition, "part" and "%" in each example are based on weight.

Production Example 1 An alcohol-modified dicyclopentadiene-based petroleum resin (“Quinton 1700”, 1-liter autoclave,
A softening point of 100 ° C., a number average molecular weight of 920, manufactured by Nippon Zeon Co., Ltd., 500 parts, and a nickel / diatomaceous earth catalyst (supporting amount of nickel: 50% by weight) of 7 parts were charged, and the temperature was kept at 260 ° C. and the hydrogen pressure was 200 kg / cm ^2. Was hydrogenated for 5 hours. Then, the obtained hydride of the alcohol-modified dicyclopentadiene-based petroleum resin was taken out, and toluene 500 was added.
200 parts after the catalyst was removed by filtering with a filter paper.
Depressurized solvent removal for 30 minutes at 20 ° C and 20 Torr gives a softening point of 1
450 parts of an alcohol-modified dicyclopentadiene-based petroleum resin hydride at 00 ° C. was obtained. Color tone of the hydride of the obtained alcohol-modified dicyclopentadiene-based petroleum resin, hydroxyl value, hydrogenation rate of unsaturated bond, number average molecular weight (M
n) and the weight average molecular weight (Mw) are shown in Table 1.

The softening point is determined by the ring and ball method (JIS K220).
It is the measured value according to 7). The color tone is based on Hazen standard color (H) and Gardner standard color (G) (JIS K5400). The hydroxyl value is determined by potentiometric titration (JIS K0070). The hydrogenation rate of the aromatic ring is determined by the proton nuclear magnetic resonance spectrum ( ¹ H-NM
It was calculated by measuring R). That is, a deuterium-substituted chloroform (CDCl ₃ solution having the same concentration as the raw material resin and the obtained hydride was prepared, ¹ H-NMR was measured, and the H-spectrum of the unsaturated double bond appearing in the vicinity of 5 to 6 ppm was obtained. It was calculated from the area based on the following formula: Hydrogenation rate = {1- (spectrum area of obtained hydride / spectrum area of raw material resin)} × 100 (%) Number average molecular weight (Mn), weight average molecular weight (Mw) is gel permeation chromatography (manufactured by Tosoh Corporation, HLC8)
02A, column used: TSKGelG4000H ₈ + T
SKGelG2000H _8, developing solvent: is measured with tetrahydrofuran).

Production Example 2 A 1 liter autoclave was charged with an alcohol-modified dicyclopentadiene-based petroleum resin (“Quinton 1700”,
A softening point of 100 ° C., a number average molecular weight of 920, manufactured by Nippon Zeon Co., Ltd., 500 parts, and a nickel / diatomaceous earth catalyst (amount of nickel carried: 50% by weight) of 10 parts were charged and kept at 280 ° C. under a hydrogen pressure of 200 kg / cm ^2. Was hydrogenated for 5 hours. Then, the obtained hydride of the alcohol-modified dicyclopentadiene-based petroleum resin was taken out, and toluene 50
After dissolving in 0 part and removing the catalyst by filter paper filtration, 20
The solvent was removed under reduced pressure at 0 ° C. and 20 Torr for 30 minutes to obtain 450 parts of an alcohol-modified dicyclopentadiene-based petroleum resin hydride having a softening point of 100 ° C. Color tone of the obtained hydride of the alcohol-modified dicyclopentadiene-based petroleum resin,
Hydroxyl value, hydrogenation rate of unsaturated bond, number average molecular weight (M
n) and the weight average molecular weight (Mw) are shown in Table 1.

[0036]

[0037]

[0038]

[Table 1]

Example 1 Polypropylene (trade name: Grand Polypro E-111,
80 parts of Grand Polymer Co., Ltd. and 20 parts of Resin A (alcohol-modified dicyclopentadiene-based petroleum resin, Quinton 1700, manufactured by Nippon Zeon Co., Ltd.) were mixed, and kneader (S1 KRC Kneader, Melt-kneaded at 200 ° C. and pelletized. Using these pellets, a polypropylene sheet was produced by a uniaxial extruder (VS40-26, manufactured by Tanabe Plastic Machinery) equipped with a T die.

Examples 2 to 3 and Comparative Examples 1 to 2 Polypropylene sheets were produced in the same manner as in Example 1 except that the kind of petroleum resin to be added was changed as shown in Table 2.

(Performance Evaluation) The polypropylene sheets obtained in each of the above Examples and Comparative Examples were evaluated by the following test methods. Further, as Comparative Example 3, the same evaluation was performed on the polypropylene sheet obtained by the same operation as in Example 1 without using various resins. The results are shown in Table 2.

(Wettability: Surface tension) The obtained polypropylene sheet was formed into a film by a biaxial stretching machine (manufactured by Iwamoto Seisakusho), and the wettability of the film was measured according to JIS K6768.

(Adhesiveness) An acrylic adhesive (Tg = -32.1 ° C.) was applied to the obtained polypropylene sheet to give a film thickness of 24.
After the polyethylene terephthalate film coated with μm was stuck, the measurement was performed according to JIS K 6854.

(Adhesion of coating film (ink)) JIS K54
The measurement was performed according to the cross-cut tape method. The paint adhesion was evaluated based on the residual rate of 100 parts. The ink used was 8 parts of resin (polyester urethane resin: reaction product of polypropylene adipate and isophorone diisocyanate), 72 parts of solvent (toluene / methyl ethyl ketone / isopropyl alcohol = 1/1/1 (% by weight)),
A mixture containing 20 parts of pigment (titanium oxide) was used.

[0045]

[Table 2]

In Table 2, resin A (alcohol-modified dicyclopentadiene petroleum resin, trade name Quinton 1700,
Nippon Zeon Co., Ltd., color tone 9G, hydroxyl value 220, softening point 100 ° C., resin B (hydrogenated petroleum resin, trade name Escorets 5300, Tonex Co., Ltd., color tone 20H,
Softening point 100 ° C, Resin C (hydrogenated petroleum resin, trade name I-MARV P-100, manufactured by Idemitsu Petrochemical Co., Ltd., color tone 20
H, softening point 100 ° C.) was used.

Claims (6)

(57) [Claims] 1. An alcohol having a hydroxyl value of 10 to 250.
A modifier for a polyolefin resin, which contains a modified petroleum resin or a hydride thereof. 2. An alcohol having a hydroxyl value of 10 to 250.
The softening point of the modified petroleum resin or its hydride is 70 to 2
The modifier for polyolefin resin according to claim 1, which has a temperature of 00 ° C. 3. An alcohol having a hydroxyl value of 10 to 250.
The number average molecular weight of the modified petroleum resin or its hydride is 2
The modifier for polyolefin resin according to claim 1 or 2, which is from 00 to 2000 . 4. A polyolefin resin (B) and a claim
Item 1. The modifier (A) according to any one of items 1 to 3 is contained.
A polyolefin resin composition. 5. Polyolefin resin (B) 100 weight
0.1 to 50 parts by weight of modifier (A)
The polyolefin resin composition according to claim 4, wherein 6. A contract having a surface tension of 33 to 39 mN / m.
The polyolefin resin composition according to claim 4 or 5.