JPH08311293A - Modified resin composition - Google Patents

Abstract

(57) [Summary] [Structure] (A) 20 to 8 acid-modified amorphous polyolefin
0 to 20 wt% and (B) 80 to 20 crystalline thermoplastic resin
A modified resin composition containing wt%. [Effect] The resin composition of the present invention is a well-balanced resin composition that is flexible in the normal temperature range and has sufficient mechanical strength in the high temperature range. Further, it has excellent adhesiveness, printability, and dyeability, and can be used as a resin modifier.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a modified resin composition, and more particularly, as a modifier for various resins having both flexibility at room temperature and sufficient mechanical strength at high temperature. Or a modified resin composition that can be used as a resin having excellent adhesiveness, printability and dyeability.

[0002]

BACKGROUND OF THE INVENTION It is known to improve the physical and chemical properties of a non-polar amorphous low molecular weight polyolefin by graft-copolymerizing an unsaturated carboxylic acid derivative. That is, by introducing a carboxyl group, the adhesiveness with a polar substance is improved, and the printability and dyeability are remarkably improved. Japanese Patent Application Laid-Open No. 1-282207 discloses a graft copolymer of an unsaturated carboxylic acid derivative onto an amorphous low molecular weight polyolefin. That is, the propylene component is 71 to 95 mol%, the ethylene component is 29 to 5 mol%, and the amorphous low molecular weight propylene-ethylene copolymer having a number average molecular weight of 3,500 to 30,000 has 3 to 3 carbon atoms. An unsaturated carboxylic acid derivative component consisting of 10 unsaturated carboxylic acids, their acid anhydrides and their esters, which is graft-copolymerized in an amount of 0.1 to 40 parts by weight per 100 parts by weight of the polymer, is used as a modifier for various resins. Alternatively, it can be used as a resin having excellent adhesiveness, printability and dyeability. Originally, amorphous low molecular weight polyolefins are often used as a main raw material for hot melt adhesives. Although the above graft copolymer is certainly sufficiently modified in terms of improving the adhesiveness, it has a low softening point and therefore can be applied only to relatively low temperature applications. That is, a material having high cohesive force and high adhesiveness from low temperature to high temperature has been desired.
Therefore, the object of the present invention is to use as a modifier of various resins having flexibility in a low temperature range and sufficient mechanical strength in a high temperature range, or as a resin excellent in adhesiveness, printability, and dyeability. Another object of the present invention is to provide a modified resin composition.

[0003]

Means for Solving the Problems As a result of intensive studies, the inventors of the present invention achieved a composition by mixing (A) an acid-modified amorphous polyolefin with (B) a crystalline thermoplastic resin. I found that

Hereinafter, the present invention will be described in detail. The amorphous polyolefin of the (A) acid-modified amorphous polyolefin in the present invention is ethylene, propylene, or C4-8.
Is a homopolymer, a binary copolymer, or a multicomponent copolymer selected from the α-olefins. Particularly preferably, propylene homopolymer, propylene-ethylene copolymer,
Propylene / butene-1 copolymer, butene-1 / ethylene copolymer, propylene / hexene-1 copolymer, propylene / 4-methyl-pentene-1 copolymer, butene-
1-hexene-1 copolymer, propylene / ethylene / butene-1 terpolymer, propylene / ethylene / hexene-1 terpolymer, propylene / ethylene-4-methyl-pentene-1 terpolymer Combined, propylene butene-
Propylene component such as 1-hexene-1 terpolymer, propylene / hexene-1 / octene-1 terpolymer, propylene / hexene-1 / 4-methyl-pentene-1 terpolymer or butene Amorphous polyolefin containing -1 component as a main component may be mentioned.

As an amorphous polypropylene,
Atactic polypropylene produced as a by-product during the production of crystalline polypropylene may be used, or it may be produced directly from a propylene raw material. In addition, propylene or butene
The copolymer of 1 with other α-olefin can be produced by using the raw material so as to contain a predetermined propylene or butene-1 component. In the case of such production, it can be obtained, for example, by polymerizing a raw material monomer in the presence or absence of hydrogen using a titanium-supported catalyst supported on magnesium chloride and triethylaluminum. From the viewpoint of supply stability and quality stability, it is desirable to use the objectively produced amorphous polyolefin. Further, a suitable and suitable commercial product can be appropriately selected and used. The amorphous polyolefin preferably has a heat of crystal fusion of 20 Joule / g or less. In the resin composition of the present invention when the heat of crystal fusion is outside the above range,
It is not preferable because it has poor flexibility near room temperature.

The heat of crystal fusion was measured as follows. That is, this heat of crystal fusion is a value calculated using a straight line obtained by directly extrapolating the specific heat curve of the polymer in a completely molten state by a differential scanning calorimeter to the low temperature side as a baseline. The measurement was carried out using a DSC-50 manufactured by Shimadzu Corporation as a differential scanning calorimeter, and the sample amount was about 10 m.
g, a nitrogen atmosphere was used as a measurement atmosphere, and indium was used as a heat quantity standard. The heating program was as follows. That is, the sample was heated to 210 ° C. at a heating rate of 50 ° C./min, left at 210 ° C. for 5 minutes, and then
Cool to -42 ° C at a cooling rate of 0 ° C / min, and leave at -42 ° C for 5 minutes. After that, at a temperature rising rate of 20 ° C / min, -40
The measurement was performed from ℃ to 200 ℃.

The amorphous polyolefin has a number average molecular weight of 2,000 to 40,000, preferably 3,0.
It is from 00 to 30,000. Number average molecular weight of 2,000
If it is less than the above range, the property as a polymer is not exhibited, and the resin composition of the present invention lacks toughness. Also,
If the number average molecular weight exceeds 40,000, the resin composition of the present invention is not preferable because the flexibility and adhesiveness at around room temperature are poor. The number average molecular weight can be measured by a known method such as gel permeation chromatography (GPC).

Further, the amorphous polyolefin has a boiling n-heptane insoluble content, that is, a Soxhlet extraction insoluble content by boiling n-heptane of 70% by weight or less, preferably 60% by weight or less, particularly preferably 10% by weight or less. Things are desirable. When the boiling n-heptane insoluble content is more than 70% by weight, the ratio of the amorphous portion is small and the resin composition of the present invention cannot have sufficient flexibility at around room temperature.

The acid-modified amorphous polyolefin (A) of the present invention comprises an unsaturated carboxylic acid derivative component consisting of an unsaturated carboxylic acid having 3 to 10 carbon atoms, its acid anhydride and its ester. At least one is a graft copolymer. The unsaturated carboxylic acid derivative component has 3 to 10 carbon atoms, and more preferably 4 to 8 carbon atoms. When the number of carbon atoms is less than 3, odor is strongly attached to the polymer, and when the number of carbon atoms exceeds 10, the graft reaction is unlikely to occur. Unsaturated carboxylic acids having 3 to 10 carbon atoms,
Examples of the unsaturated carboxylic acid derivative composed of the acid anhydride and the ester thereof include acrylic acid, methacrylic acid, maleic acid, fumaric acid, itaconic acid, citraconic acid, tetrahydrophthalic acid, bicyclo (2,2,1) hept- Unsaturated carboxylic acids such as 2-ene-5,6-dicarboxylic acid, maleic anhydride, itaconic anhydride, citraconic anhydride, tetrahydrophthalic anhydride, bicyclo (2.
2,1) Anhydrides of unsaturated carboxylic acids such as hept-2-ene-5,6-dicarboxylic acid anhydride, methyl acrylate, methyl methacrylate, dimethyl maleate, monomethyl maleate, diethyl fumarate, itaconic acid Dimethyl, diethyl citraconic acid, dimethyl tetrahydrophthalate, bicyclo (2,2,1) hept-2-ene-
Mention may be made of esters of unsaturated carboxylic acids such as dimethyl 5,6-dicarboxylate. Among these, maleic acid,
Itaconic acid or anhydrides thereof are preferred.

The graft copolymerization is carried out by a known method. For example, the organic peroxide is added to a molten mixture of an amorphous polyolefin and an unsaturated carboxylic acid derivative component or to a solution using a solvent such as toluene or xylene. Further, ionizing radiation such as γ-rays may be irradiated without adding the organic peroxide. In any case, it is preferable to avoid mixing of air and oxygen in this graft copolymerization, and it is desirable to carry out in an atmosphere of an inert gas such as nitrogen gas or carbon dioxide gas.

The organic peroxide preferably has a decomposition temperature in the range of 70 to 270 ° C., which has a half-life of 1 minute, and includes, for example, acetylcyclohexylsulfonyl peroxide, benzoyl peroxide, dichlorobenzoyl peroxide, dicumyl peroxide. , The -tert-
Butyl peroxide, 2,5-dimethyl-2,5-di (tert-butylperoxy) hexyne-3,1,4
-Bis (tert-butylperoxyisopropyl) benzene, lauroyl peroxide, tert-butylperoxyacetate, 2,5-dimethyl-2,5-di (tert-butylperoxy) hexane, tert-
Butyl peroxybenzoate, tert-butyl peroxylaurate, tert-butyl peroxyisobutyrate, tert-butyl peroxypivalate, cumyl peroxy octoate, tert-butyl peroxy (2-ethylhexanoate), tert-butyl hydroperoxide , Tert-butyl peroxyisopropyl monocarbonate, cumene hydroperoxide and the like.

The graft copolymerization temperature when an organic peroxide is used depends on the softening point of the amorphous polyolefin and the decomposition temperature of the organic peroxide, but is generally 80 to 220 ° C.

The blending amount of the unsaturated carboxylic acid derivative component and the organic peroxide, and the temperature and time of the graft copolymerization are such that the acid value of the obtained (A) acid-modified amorphous polyolefin is 1 to 200.
mgKOH / g, preferably 1-100 mgKOH / g
Is selected as appropriate. Here, the acid value is the number of mg of KOH required for neutralization per 1 g of the polymer, and in this case, (A) the carboxylic acid group and / or carboxylic acid anhydride group in the acid-modified amorphous polyolefin and / Or corresponds to a standard of the concentration of the ester group. When the acid value of the acid-modified amorphous polyolefin (A) is less than 1, the polarity is insufficient and the resin composition of the present invention does not exhibit adhesiveness and the like. Further, if it is attempted to obtain more than 200, side reactions such as main chain cleavage or cross-linking of the amorphous polyolefin will not occur and effective modification will not occur, so that more than 200 is practically not preferable. Of course, as the (A) acid-modified amorphous polyolefin of the present invention, a suitable commercial product can be appropriately selected and used.

The crystalline thermoplastic resin (B) in the present invention is a polyolefin resin such as polyethylene, polypropylene or poly-4-methylpentene-1, nylon 6, nylon 66, nylon 11, nylon 12, nylon 6
Polyamide resin such as 10, nylon 6/66, nylon 6/11, nylon 6/12, nylon 6/66/1
1, a copolymerized polyamide resin such as nylon 6/66/12, a polyester resin such as polyethylene terephthalate and polybutylene terephthalate, a polyacetal resin, and the like, and a polyolefin resin, a polyamide resin, and a polyester resin are preferable.

The mixing ratio of (A) the acid-modified amorphous polyolefin and (B) the crystalline thermoplastic resin is (A) 20.
８０80% by weight, preferably 30-70% by weight.
If (A) is less than 20% by weight, Shore D hardness H at room temperature
Since s (23 ° C.) exceeds 60, sufficient flexibility cannot be obtained. On the other hand, when (A) exceeds 80% by weight, Shore D
The hardness Hs (23 ° C) is less than 8, which is too soft at room temperature,
The tensile elastic modulus (80 ° C.) at 80 ° C. is less than 30 kg / cm ² , the shape cannot be sufficiently retained, and the mechanical strength cannot be maintained.

The resin composition of the present invention is obtained by blending the components (A) and (B) within the above range, and preferably,
The Shore D hardness Hs (23 ° C.) is 8 or more and 60 or less, and the tensile elastic modulus (80 ° C.) is 30 kg / cm ² or more and less than 2,000 kg / cm ² . In the present invention, the Shore D hardness Hs (23 ° C) and the tensile elastic modulus (80 ° C) were measured by the following methods. The resin composition is (A) a softening point of the acid-modified amorphous polyolefin,
(B) A pressing pressure of 100 kg / c at a temperature 20 ° C. higher than the higher of the melting points of the crystalline thermoplastic resin.
m ^2, 2 minutes preheating, 1 minute pressed and molded into a sheet having a thickness of 2mm by press molding at a cooling 3 minutes. (Shore D hardness Hs
(23 ° C.)) The sheet obtained as described above is heated to 23 ° C.
After adjusting in a thermostatic chamber, press the hardness tester from the top of the 6 sheets,
The value after 5 seconds was measured. (Tensile Elastic Modulus (80 ° C.)) The sheet obtained as described above was punched with a JIS No. 2 type dumbbell to obtain a tensile test piece. The obtained test piece having a cross-sectional area Scm ² was placed in a constant temperature bath at 80 ° C. and a crosshead speed of 50.
mm / min, chuck distance 5 cm, chart speed 50c
A tensile test was performed at m / min, and the tensile load Xkg at 2% deformation was measured while reading the displacement between the chucks on the chart. From the obtained results, the tensile elastic modulus (80 ° C.) was calculated by the following formula. Tensile elastic modulus (80 ° C) (kg / cm ² ) = X / S / 2 /
100 = 100X / 2S

In the modified resin composition,
The acid value is 0.2 to 160 mgKOH / g, preferably 0.2 to 100 mgKOH / g. Therefore, the blending amounts of (A) and (B) are determined according to the acid value of (A) so that the acid value of the composition falls within the above range.
When the acid value of the composition is less than 0.2, the adhesiveness is poor and there is no modifying effect. The adhesive strength was measured as follows.
That is, the modified composition was sandwiched between adherends and heat-bonded by a hot press under a pressure of 50 kg / cm ² . It is cut to a width of 25 mm, and the tensile speed is 200 m in a constant temperature room at 23 ° C.
The T peel strength was measured in m / min. The temperature of the hot press is (A) the softening point of the acid-modified amorphous polyolefin,
(B) The temperature was 20 ° C. higher than the higher temperature of the melting point of the crystalline thermoplastic resin.

For industrially producing the composition of the present invention,
An extruder is preferably used. A single-screw or multi-screw extruder with a vent can be used as the extruder. In this case, if there is a suitable one as the (A) acid-modified amorphous polyolefin, it may be directly supplied to the extruder and melt-kneaded with the (B) crystalline thermoplastic resin. Alternatively, the amorphous polyolefin may be acid-modified in an extruder as described below, and then (B) the crystalline thermoplastic resin may be melt-kneaded in the extruder.

(Manufacturing Process) Amorphous polyolefin, organic peroxide and unsaturated carboxylic acid derivative components are simultaneously or separately charged from a hopper or a vent using a plurality of twin-screw extruders with vents. The cylinder temperature is determined by the softening point of the amorphous polyolefin and the decomposition temperature of the organic peroxide. Generally, the temperature is 80 to 220 ° C., and the graft copolymerization is almost completed by the melt kneading for 20 seconds to several minutes.

In general, amorphous polyolefin has a strong adhesive property and is difficult to be pelletized, so that it cannot be directly charged from a hopper. Therefore, it is preferable to heat and melt and supply from a hopper or a vent port with a metering pump. At this time, the melting and supplying temperature is preferably 20 ° C. or higher, more preferably about 120 to 220 ° C., from the softening point of the amorphous polyolefin. In this case, the unsaturated carboxylic acid derivative component is
For example, maleic anhydride (white flakes or granules at room temperature with a melting point of 53 ° C. and a boiling point of 202 ° C.) undergoes remarkable sublimation at high temperatures, so avoid blending with molten amorphous polyolefin and supplying it. It is preferable to feed from C ₀ to C ₁ separately from the molten amorphous polyolefin.

The organic peroxide is selected according to the softening point of the amorphous polyolefin used. Since the decomposition half-life of the organic peroxide has a value determined by the temperature, when graft-copolymerizing with an amorphous polyolefin having a low softening point, an organic peroxide having a low decomposition half-life temperature, for example, ter
t-butylperoxy (2-ethylhexanoate)
[Perbutyl O, manufactured by NOF CORPORATION, decomposition half-life 1 minute temperature: 135 ° C.] is also used in the case of graft copolymerization with an amorphous polyolefin having a high softening point, an organic peroxide having a high decomposition half-life temperature. An oxide such as tert-butyl peroxybenzoate [Perbutyl Z, manufactured by NOF CORPORATION, decomposition half-life 1 minute temperature: 170 ° C.] is selected. The organic peroxide is quantitatively supplied from a position where the amorphous polyolefin and the unsaturated carboxylic acid derivative components are melt-kneaded and mixed with each other in the extruder in order to ensure uniform graft copolymerization. Is preferred.

During this period, the intermediate vent port is degassed under reduced pressure to remove unreacted unsaturated carboxylic acid derivative components. Degas using a vacuum pump with a trap for 20 m
The pressure is reduced to about mHg. In addition, in order to perform this removal efficiently, it is necessary to keep the system in a molten state. Usually, it is 20 from the softening point of amorphous polyolefin.
C. or higher, preferably about 120 to 220.degree.

Next, (B) the crystalline thermoplastic resin is supplied from a vent port located after the acid modification zone, and (A)
The acid-modified amorphous polyolefin and (B) the crystalline thermoplastic resin are melt-kneaded. The temperature of the melt-kneading zone of the (A) acid-modified amorphous polyolefin and the (B) crystalline thermoplastic resin is (A) the acid-modified amorphous polyolefin softening point,
(B) The melting point of the crystalline thermoplastic resin is higher than the higher temperature, which is about 120 to 300 ° C.

In the present invention, various additives, reinforcing materials, fillers such as heat stabilizers, antioxidants, light stabilizers, antistatic agents, lubricants, nucleating agents, flame retardants, pigments, or Dye, glass fiber, magnesium sulfate fiber (MO
S), zonotolite fiber, carbon fiber, calcium carbonate,
Calcium sulfate, barium sulfate, magnesium hydroxide,
Mica, talc, clay, etc. can be added.
The modified resin composition of the present invention is excellent in adhesiveness, printability and dyeability as a modifier of various resins having both flexibility at room temperature and sufficient mechanical strength at high temperature. It can be widely used as a resin.

[0025]

[Examples and Comparative Examples]

 Example 1 Cylinder block C₀~ C₁₇Twin-screw extruder with
Part Kosan Co., Ltd. twin-screw extruder, inner diameter 55 mm, L / D =
60) was used. Ube as an amorphous polyolefin
Amorphous propylene / ethylene copolymer manufactured by Xen Co., Ltd.
Ubetac UT-2535 (Propylene component 85 weight
%, Number average molecular weight 4700, softening point 129 ° C., crystal melting
Heat quantity 10 Joule / g) is melted to 150 ℃,
Block C₀It is supplied at a rate of 10 kg / hour from the inlet provided in
Was. Further, as an unsaturated carboxylic acid derivative component,
Molten maleic anhydride (Crystalman, NOF Corporation)
Perbutyl Z at room temperature as an organic peroxide
This oil and fat Co., Ltd., decomposition half-life 1 minute temperature: 170 ℃)
Cylinder block C ₀, C₃From the inlet provided in
It was supplied at 0.1 kg and 0.1 kg per hour, respectively. In addition,
Linder block C₁₁The vent port provided in is about 20m
Degas under reduced pressure to mHg to remove unreacted maleic anhydride.
Was.

Next, (B) as a crystalline thermoplastic resin, polypropylene RF355B (MFR manufactured by Ube Industries, Ltd.)
= 2.7, ethylene component 4% by weight, melting point 138 ° C.)
_It was supplied at 10 kg / hour from ₁₂ vent ports. The acid value of the obtained modified resin composition is 5 mgKOH / g, 23 ° C.
Has a Shore D hardness Hs (23 ° C.) of 41, a tensile elastic modulus at 80 ° C. of 360 kg / cm ² , and a T-peel strength of 4.3 k between aluminum sheets (thickness 100 μm) at room temperature.
It was g / 25 mm. The raw material composition, cylinder temperature and results are shown in Table 1.

Example 2 In Example 1, except that (B) the crystalline thermoplastic resin was replaced with linear low-density polyethylene (Ultzex 2022L, manufactured by Mitsui Nisseki Polymer Co., Ltd.), and the cylinder set temperature was changed. Was performed in the same manner as in Example 1. The results are shown in Table 1.

Example 3 In Example 1, the amorphous polyolefin was replaced by an amorphous propylene / butene-1 copolymer Ubetac UT-2780 (65% by weight of propylene component, manufactured by Ube Lexen Co., Ltd.).
Number average molecular weight 6500, softening point 110 ° C, heat of crystal fusion 7 Joule / g), and change the supply temperature,
(B) The same procedure as in Example 1 was performed except that the crystalline thermoplastic resin was changed to nylon 12 (UBE nylon 3030U, manufactured by Ube Industries, Ltd.) and the cylinder set temperature was changed.
The results are shown in Table 1.

[0029]

[Table 1]

Comparative Example 1 The procedure of Example 1 was repeated, except that the (B) crystalline thermoplastic resin was not supplied. The acid value of the obtained composition was 10 mgKOH / g, aluminum / aluminum T-
The peel strength was 4.1 kg / 25 mm, but Hs (2
3 ° C) is 2 and too soft, and the tensile modulus (80 ° C)
Was also too small at 10 kg / cm ² . Table 2 shows the results.

Comparative Example 2 (B) As a crystalline thermoplastic resin, polypropylene RF was used.
Only 355B was evaluated. Both Hs (23 ° C.) and tensile modulus (80 ° C.) were too large, and the aluminum / aluminum T-peel strength was 0.2 kg / 25 mm, which was extremely low. Table 2 shows the results.

Comparative Examples 3 and 4 The same procedures as in Examples 1 and 2 were carried out, except that maleic anhydride and organic peroxide were not supplied. The Hs (23 ° C.) and the tensile elastic modulus (80 ° C.) of the obtained composition were within the desired ranges, but the acid value was 0 mgKOH / g, and the aluminum / aluminum T-peel strength was 0.3 each. , 0.2 kg / 25 mm, which was extremely low. Table 2 shows the results.

Comparative Example 5 The procedure of Example 3 was repeated except that maleic anhydride and organic peroxide were not supplied. The compositions discharged from the nozzles were not mixed with each other and could not be said to be uniform compositions, and were not worth further evaluation of physical properties. Table 2 shows the results.

[0034]

[Table 2]

[0035]

The resin composition of the present invention is a well-balanced resin composition that is flexible in the normal temperature range and has sufficient mechanical strength in the high temperature range. Further, it has excellent adhesiveness, printability, and dyeability, and can be used as a resin modifier.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Masaru Kunimura 3-10 Nakamiyakitamachi, Hirakata-shi, Osaka Ube Industries, Ltd. Hirakata Research Laboratory (72) Iwa Tsuruya 2-3-11 Higashishinagawa, Shinagawa-ku, Tokyo No. UBE Building 5F Ube Lexen Co., Ltd.

Claims (3)

[Claims] 1. An acid-modified amorphous polyolefin (A) is 20
-80% by weight and (B) 80% crystalline thermoplastic resin
A modified resin composition containing 20% by weight. 2. The amorphous polyolefin of the acid-modified amorphous polyolefin has ethylene, propylene, and 4 to 4 carbon atoms.
A homopolymer, a binary copolymer or a multicomponent copolymer selected from α-olefins of 8 and having a number average molecular weight of 2,
000-40,000, and the heat of fusion of crystal is 20
The modified resin composition according to claim 1, having a Joule / g or less. 3. An acid-modified amorphous polyolefin is graft-copolymerized on an amorphous polyolefin with at least one unsaturated carboxylic acid derivative component consisting of an unsaturated carboxylic acid having 3 to 10 carbon atoms, its acid anhydride and its ester. The modified resin composition according to claim 1, having an acid value of 1 to 200 mgKOH / g.