JPH1077374A - Propylene resin composition, modified propylene resin composition and production of the composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a polypropylene resin composition improving the transparency and processability of a polypropylene resin or the transparency, processability and impact resistance of the polypropylene resin. SOLUTION: This polypropylene resin composition comprises 10-99.99wt.% of a branched propylenic resin obtained by the branching and crosslinking reaction of a linear propylenic resin and having a branching parameter of 0.9-0.1, 0.01-90wt.% of a crosslinked propylenic resin, and further a polyolefin rubber having the substantially same refractive index as that of linear polypropylene, when improving impact resistance.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention belongs to the technical field of producing and using propylene resin compositions and modified propylene resin compositions. More specifically, it belongs to the technical field of producing and using a propylene-based resin composition having excellent transparency and processability and a modified propylene-based resin composition having excellent transparency, processability and impact resistance.

[0002]

2. Description of the Related Art Polypropylene has a good balance of physical properties such as rigidity, heat resistance and chemical resistance, but has poor transparency due to high crystallinity, and its extrusion molded sheet, calender molded sheet, vacuum molding of the sheet, and compressed air. The transparency of thermoformed articles such as molding, injection molded articles, blow molded bottles, etc. is also low. Further, since the crystallinity is high, the sag resistance required at the time of processing is small, and workability such as thermoforming, calendering, and direct blow molding of a sheet is poor. Furthermore, impact resistance is not always sufficient.

Hitherto, a nucleating agent has been generally added to improve the transparency of polypropylene, and a certain effect has been obtained by using an organic nucleating agent.

[0004] In addition, in order to improve the processability of polypropylene, polyethylene has been generally added.

[0005] Further, in order to improve the impact resistance of polypropylene, addition of a polyolefin rubber has been generally performed.

[0006]

However, when the transparency is improved by using the above-mentioned organic nucleating agent, bleed-out is liable to occur in the case of a low molecular weight substance having relatively high transparency. It has the drawbacks that odor due to the body is generated and that neither processability nor impact resistance is improved.

On the other hand, in the case of a high molecular nucleating agent in which the problems of bleed-out and odor are improved, there are few problems of bleed-out and odor, but high transparency cannot be obtained.
It still has the disadvantage that neither processability nor impact resistance is improved.

When the processability is improved by the addition of the polyethylene, the transparency is reduced when the refractive indices of the polypropylene and the polyethylene are different, and even when the refractive indices of the polypropylene and the polyethylene are equal, the transparency is reduced. It has the disadvantage that transparency is not improved.

Further, when the impact resistance is improved by the addition of the polyolefin rubber, if the refractive index of the polypropylene is different from that of the polyolefin rubber, the transparency is reduced, and the refractive index of the polypropylene and the polyolefin rubber is reduced. However, even if they are equal, they have the disadvantage that their transparency is not improved and their processability is not improved.

[0010] The present invention provides a propylene-based resin composition having both high transparency and processability, and hardly bleeding out.
Further, it is intended to obtain a propylene-based resin composition having both impact resistance.

[0011]

Means for Solving the Problems The present inventors have conducted intensive studies in view of the above-mentioned circumstances, and as a result, have found that a composition of a propylene resin having a specific branching parameter and a specific crosslinked propylene resin or The composition of the propylene-based resin and the propylene-based resin composition gives a molded article having excellent transparency and processability, and the higher the content of the branched and crosslinked propylene-based resin, the higher the transparency and processability. In addition, when a polyolefin rubber having a refractive index substantially equal to that of the linear polypropylene is further added to the two compositions, the resulting composition has excellent transparency and processability, and It has been found that a molded article having excellent impact resistance is provided.

The present invention has been made based on the above findings, and has a branching parameter of 0.9 to 0.1 obtained by a branching and crosslinking reaction of a linear propylene resin.
10 to 99.99% (weight%, the same applies hereinafter) of a branched propylene-based resin and a crosslinked propylene-based resin 0.01 to 0.01
Propylene resin composition (I) comprising 90% (claim 1), propylene resin composition (II) comprising 99 to 1% of linear propylene resin and 1 to 99% of propylene resin composition (I) ) (Claim 2), a polyolefin rubber 1 having 90 to 10% of a propylene resin composition (I) and a refractive index substantially equal to that of a linear polypropylene.
0 to 90% of a modified propylene resin composition (II
I) (claim 3), propylene-based resin composition (II) 99
A modified propylene-based resin composition (IV) comprising 1 to 50% of a polyolefin rubber having a refractive index substantially equal to that of a linear polypropylene (claim 4),
The propylene resin according to claim 1, wherein the branching and crosslinking reaction of the linear propylene resin is a branching and crosslinking reaction of a silylated propylene resin obtained by graft copolymerizing a silyl group-containing monomer with the linear propylene resin. The composition (I) (Claim 5), wherein the branching and crosslinking reaction of the linear propylene resin is a branching and crosslinking reaction with the linear propylene resin, a divinyl aromatic monomer and a radical polymerization initiator. The propylene-based resin composition (I) according to claim 1 (Claim 6), a silylated propylene-based resin obtained by graft-copolymerizing a silyl group-containing monomer to a linear propylene-based resin is subjected to a branching and crosslinking reaction in a melt-kneaded state. The method for producing the propylene resin composition (I) according to claim 1 (claim 7), a linear propylene resin, and divinyl. 2. The process for producing a propylene-based resin composition (I) according to claim 1, wherein the aromatic monomer and the radical polymerization initiator are subjected to branching and crosslinking reaction in a melt-kneaded state. The propylene-based resin composition according to claim 2, wherein the silylated propylene-based resin obtained by graft-copolymerizing a silyl group-containing monomer with a linear resin and a linear propylene-based resin is subjected to branching and crosslinking reaction in a melt-kneaded state. Thing (II)
Melt-kneading a silylated propylene resin obtained by graft copolymerizing a silyl group-containing monomer to a linear propylene resin and a polyolefin rubber having a refractive index substantially equal to that of linear polypropylene. 4. The method for producing a modified propylene resin composition (III) according to claim 3, wherein the silylated propylene resin is subjected to a branching and crosslinking reaction in a state thereof, and a linear propylene resin. Resin, a silylated propylene-based resin obtained by graft copolymerizing a silyl group-containing monomer to a linear propylene-based resin, and a polyolefin-based rubber having a refractive index substantially equal to that of linear polypropylene, in a melt-kneaded state. 5. The modified propylene-based resin according to claim 4, wherein a branching and crosslinking reaction of the resin is carried out. Preparation of the composition (IV) (claim 1
Regarding 1).

[0013]

BEST MODE FOR CARRYING OUT THE INVENTION The propylene resin composition (I) (hereinafter also referred to as PP composition (I)) of the present invention is a linear propylene resin (hereinafter also referred to as linear PP resin).
Of a branched propylene resin (hereinafter also referred to as a branched PP resin) having a branch parameter of 0.9 to 0.1, preferably 0.7 to 0.3 obtained by the branching and crosslinking reaction of
To 99.99%, preferably 30 to 99.99%, and a crosslinked propylene resin (hereinafter, also referred to as a crosslinked PP resin).
Is 0.01 to 90%, preferably 0.01 to 70%. As described above, when the PP-based composition (I) has a branching parameter of 0.9 to 0.9 obtained by a reaction in which the branching reaction and the crosslinking reaction of the linear PP-based resin occur together.
Since the branched PP-based resin of 0.1 is a mixture of 10 to 99.99% and the cross-linked PP-based resin is 0.01 to 90%, branching and cross-linking occurred as compared with the linear PP-based resin. Minutes,
It is thought that entanglement between molecules is likely to occur, and it is thought to exhibit the action of a nucleating agent.The transparency is improved by reducing the size and diameter of the crystal, and the sag resistance required during processing is also reduced. growing.

The linear PP resin is at least one of a propylene homopolymer (polypropylene) and a random copolymer, and has a crystallinity of 90% as isotactic pentad content. More than 95%
Above and below 100%, melt index 0.1 g /
10 minutes or more, and 0.2 g / 10 minutes or more, usually 10 minutes
0g / 10min or less, 0.9 when the branching parameter is 1 or less
That is, those having a linear propylene-based resin and those having some branches but not having enough branches to achieve the object of the present invention. In addition,
Even when a linear PP resin is introduced with a functional group in order to cause a branching or cross-linking reaction, the branching parameter is 0.1.
Those exceeding 9 are included in the category of linear PP resins.

The isotactic pentad is 90%
If less than, the content of the atactic polymer increases,
The crystallinity, rigidity, heat resistance, and chemical resistance of the linear PP resin decrease. The melt index is 0.1.
Those with less than 1 g / 10 min are difficult to obtain on the market and are economically expensive, while those with more than 100 g / 10 min have reduced crystallinity, rigidity, heat resistance and chemical resistance of the linear PP resin. I will.

As the random copolymer of propylene, one containing 75% or more, particularly 90% or more of propylene, has a crystallinity characteristic of a linear PP resin,
It is preferable because rigidity, heat resistance, chemical resistance and the like are maintained.

Examples of monomers copolymerizable with propylene constituting the random copolymer of propylene include ethylene, butene-1, isobutene, pentene-1, 3-
Methylbutene-1, hexene-1, 4-methylpentene-1,3,4-dimethylbutene-1, heptene-1,3
Α-olefins having 2 or 4 to 12 carbon atoms, such as methylhexene-1, octene-1, decene-1, cyclic olefins such as cyclopentene and norbornene, 5-methylene-2-norbornene, 5-ethylidene-2-norbornene , 1,4-hexadiene, methyl-1,4-hexadiene, diene such as 7-methyl-1,6-octadiene, vinyl chloride, vinylidene chloride, acrylonitrile, vinyl acetate, acrylic acid, methacrylic acid, maleic acid, acrylic acid Examples thereof include vinyl monomers such as ethyl, butyl acrylate, glycidyl acrylate, methyl methacrylate, glycidyl methacrylate, maleic anhydride, styrene, methylstyrene, vinyltoluene, and divinylbenzene. These may be copolymerized singly.
Copolymers may be used in combination of two or more kinds. Of these, ethylene and butene-1 are preferred from the viewpoints of giving a polymer with good transparency and being inexpensive.

Specific examples of the random copolymer of the copolymer component and propylene as described above include, for example, a propylene-ethylene copolymer and a propylene-butene-1 copolymer.

The shape and size of the linear PP resin are not limited, and may be in the form of particles or pellets.

When the crosslinked PP resin is contained, the above-mentioned branched PP resin is obtained by excluding it as a hot xylene-insoluble component, that is, in a high temperature GPC measurement (column temperature 140 ° C.) of the hot xylene-soluble component. Calculated from the chromatogram of the RI detector and the chromatogram of a viscometer directly connected to GPC by the multi-director GPC software Ver3.00 (manufactured by Nippon Waters Limited), and the branch parameter according to the value in the weight average molecular weight is 0.9 to 0. 1.1 PP-based resin. When the branching parameter exceeds 0.9, the effect of the present invention cannot be sufficiently obtained even if a PP-based resin having a branch in this range is used.

The above-mentioned crosslinked PP resin is obtained by putting a PP resin obtained by a branching and crosslinking reaction into a 10 μm polyflon filter bag and dissolving it in a 600-fold weight xylene at 130 ° C. for 6 hours. After that, it is a PP-based resin for a gel portion remaining in a bag of a 10 μm polyflon filter.

The degree of branching in the branched propylene resin or the degree of crosslinking in the crosslinked propylene resin is 0.9 or less, preferably 0.7 or less.
Or less, or a gel fraction of 0.1% or more, preferably 1%
The above is preferable from the viewpoint of acting as a nucleating agent and increasing the sag resistance.

The PP composition (I) is, for example, a linear P
A linear PP resin, divinyl, which is obtained by graft-copolymerizing a silyl group-containing monomer with a P-based resin (hereinafter, also referred to as a silylated PP resin) in a melt-kneaded state to cause a branching and crosslinking reaction. It can be produced by a method of bringing a mixture of an aromatic monomer and a radical polymerization initiator into a melt-kneaded state and causing a branching and crosslinking reaction.

Specific examples of the silyl group-containing monomer used for producing the silylated PP resin include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltributoxysilane, vinyltriacetoxysilane, and 3-triacetoxysilane.
Methacryloyloxypropyltrimethoxysilane, 3
-Methacryloyloxypropylmethyldimethoxysilane, vinyltris (2-methoxyethoxy) silane, trimethylsilylvinylbicyclo [2,2,1] heptane, N, N-bis [(methyldimethoxysilyl) propyl] methacrylamide, N, N-bis [(Trimethoxysilyl) propyl] methacrylamide, vinyltrimethoxysilylbenzene and the like, and a monomer containing a silanol group generated by hydrolysis of these alkoxysilyl groups are also included.

The amount of the silyl group-containing monomer used is as follows:
0.01 to 15 parts with respect to 100 parts of the linear PP resin,
Preferably it is 0.1 to 10 parts. When the amount of the silyl group-containing monomer used is less than 0.01 part, the silylated PP-based resin is less likely to branch and crosslink, and the effect of improving transparency and processability is reduced. .

The radical polymerization initiator used for graft copolymerizing a silyl group-containing monomer with a linear PP resin is, for example, 1,1-bis (t-butylperoxy) 3,3,5-trimethyl. Cyclohexane, 1,1
-Bis (t-butylperoxy) cyclohexane, n-
Peroxyketals such as butyl 4,4-bis (t-butylperoxy) valerate and 2,2-bis (t-butylperoxy) butane; dicumyl peroxide;
5-dimethyl-2,5-di (t-butylperoxy) hexane, α, α'-bis (t-butylperoxy-m-
Isopropyl) benzene, t-butylcumyl peroxide, di-t-butyl peroxide, 2,5-dimethyl-2,5-di (t-butylperoxy) hexyne-3
Dialkyl peroxide such as benzoyl peroxide, t-butyl peroxy octate, t-butyl peroxyisobutyrate, t-butyl peroxy laurate, t-butyl peroxy-3,5, 5-trimethylhexanoate, t-
Butyl peroxyisopropyl carbonate, 2,5-
Peroxides such as dimethyl-2,5-di (benzoylperoxy) hexane, t-butylperoxyacetate, t-butylperoxybenzoate, and di-t-butylperoxyisophthalate; Examples include azo compounds such as lonitrile and methyl azoisobutyrate.

The amount of the radical polymerization initiator is 0.01 to 5 parts, preferably 0.01 to 2 parts, per 100 parts of the linear PP resin.

In the graft copolymerization, if necessary, for example, 2,6-di-t-butyl-4-methylphenol, 2,2'-methylene-bis- (4-methyl-6-t
-Butylphenol), 4,4'-methylidene-bis-
(3-methyl-6-t-butylphenol), 4,4 '
-Thiobis- (3-methyl-6-t-butylphenol), octadecyl-3- (3,5-di-t-butyl-
4-hydroxyphenyl) propionate, tetrakis- [methylene-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] methane, 6-
(3,5-di-t-butyl-4-hydroxyanilino)
-2,4-bis-octylthio-1,3,5-triazine, tris- (3,5-di-t-butyl-4-hydroxybenzyl) isocyanurate, dilaurylthiodipropionate, distearylthiodipropion An antioxidant such as a catenate or trisnonylphenyl phosphite may be added.

The amount of the antioxidant is selected from linear PP
0.005 to 10 parts, preferably 0.01 to 5 parts, per 100 parts of the system resin.

Conditions for the reaction in a molten state are, for example, 130 to 300 ° C., and 160 ° C.
At a temperature of about 250 ° C. for 1 to 60 minutes,
Conditions such as kneading and reaction for about 10 minutes are exemplified.

At the time of the branching and crosslinking reaction, an appropriate amount of water
For example, water 0.1 to 100 parts of silylated PP resin
It is preferred to add 100 parts. The amount of water is 0.1
If the amount is less than 100 parts, branching and crosslinking may not be sufficient. If the amount exceeds 100 parts, the resin temperature may be lowered by water cooling, and the silylated PP resin may be crystallized. Further, a catalyst for accelerating the branching and crosslinking reaction such as dibutyltin dilaurate, dibutyltin diacetate, dibutyltin dioctate and the like may be added. The amount of the catalyst to be added is preferably 0.001 to 10 parts, more preferably 0.1 to 5 parts, per 100 parts of the silylated PP resin.

Specific examples of the silylated PP resin as described above include, for example, Wrinklon manufactured by Mitsubishi Chemical Corporation.

The divinyl aromatic monomer used for producing the PP composition (I) using a mixture of a linear PP resin, a divinyl aromatic monomer and a radical polymerization initiator includes, for example, Divinylbenzene is preferred because it can improve transparency and processability.

The amount of the divinyl aromatic monomer used is 0.1 to 1 based on 100 parts of the linear PP resin.
0 parts, more preferably 0.2 to 5 parts, is preferable in that the transparency improving effect is large and economical.

As the radical polymerization initiator used for reacting the divinyl aromatic monomer with the linear PP resin, peroxides and azo compounds are generally preferred. In order for a graft reaction to occur between the linear PP resin and the divinyl aromatic monomer or the linear PP resin, it is necessary to have a so-called hydrogen abstraction ability. Organic peroxides such as ketals, hydroperoxides, dialkyl peroxides, diacyl peroxides, peroxydicarbonates, peroxyesters and the like can be mentioned. Among them, those having a particularly high hydrogen abstracting ability are preferable. For example, 1,1-bis (t-butylperoxy)
3,3,5-trimethylcyclohexane, 1,1-bis (t-butylperoxy) cyclohexane, n-butyl4,4-bis (t-butylperoxy) valerate,
Peroxyketals such as 2,2-bis (t-butylperoxy) butane; dicumyl peroxide;
Dimethyl-2,5-di (t-butylperoxy) hexane, α, α′-bis (t-butylperoxy-m-isopropyl) benzene, t-butylcumyl peroxide, di-t-butylperoxide, Dialkyl peroxides such as 2,5-dimethyl-2,5-di (t-butylperoxy) hexyne-3, dialsyl peroxides such as benzoyl peroxide, t-butylperoxyoctate, t-butylperoxyiso Butyrate, t-butylperoxylaurate, t-butylperoxy-3,5,5-trimethylhexanoate, t-
Butyl peroxyisopropyl carbonate, 2,5-
Examples include peroxyesters such as dimethyl-2,5 di (benzoylperoxy) hexane, t-butylperoxyacetate, t-butylperoxybenzoate, and di-t-butylperoxyisophthalate.

The amount of the radical polymerization initiator to be used is 0.05 to 5 based on 100 parts of the linear PP resin.
Part, more preferably 0.1 to 2 parts, is preferable from the viewpoint that the effect of improving transparency is large and economical.

The conditions for crosslinking the above-mentioned linear PP resin, divinyl aromatic monomer and radical polymerization initiator in a molten state are, for example, a temperature of about 130 to 300 ° C., more preferably about 160 to 250 ° C. 1 to 60 minutes,
Further, conditions such as kneading and reaction for about 1 to 10 minutes are exemplified.

When the linear PP resin, the divinyl aromatic monomer and the radical polymerization initiator are branched and cross-linked in a molten state, the divinyl aromatic monomer and the radical polymerization initiator are combined with the linear PP resin. In order to disperse them uniformly in the system, aromatic compounds such as xylene, toluene and benzene, aliphatic compounds such as octane, heptane, hexane, pentane and butane, and oils such as cyclooctane, cycloheptane, cyclohexane, cyclopentane and cyclobutane A dispersion medium such as a cyclic compound may be added to the divinyl aromatic monomer or the radical polymerization initiator. The amount of the dispersing medium to be used is preferably 1 to 50 parts, especially 2 to 30 parts, per 100 parts of the linear PP-based resin, since the transparency improving effect is large and economical.

The proportion of the branched PP resin and the crosslinked PP resin in the PP composition (I) is 10 to 99.99%, more preferably 30 to 99.99%, for the branched PP resin.
Crosslinked PP resin 0.01 to 90%, further 0.01 to 90%
A composition comprising 70% is preferred from the viewpoint of transparency and processability.

When a molded article is manufactured using the PP composition (I) as described above, good rigidity, heat resistance, chemical resistance, etc., which are characteristics of the case of using a linear PP resin, are obtained. A molded product having both high transparency and processability and hardly bleeding out can be manufactured without generating the odor generated when a low molecular weight organic nucleating agent is used. . Although the details of the cause of the high transparency are not clear, the branched and crosslinked PP
This is considered to be the result of the nucleation action of the resin.

The PP composition (I) may be used alone for the production of molded articles, but may be further blended with a linear PP resin to form a propylene resin composition (II) (hereinafter referred to as PP (Also referred to as composition (II)).

When the PP composition (I) is used in combination with a linear PP resin, the linear PP resin 99 to 1
%, More preferably 99 to 50%, and the PP-based composition (I) 1 to 9
It is easy to prepare the PP-based composition (II) by blending so as to be a composition consisting of 9%, and further 1 to 50%,
It is preferable from the economical point that transparency and processability are improved. Thus, the PP composition (I) can be used as a modifier for the transparency and processability of the linear PP resin. Furthermore, the PP composition (II) can also be used as a modifier for the linear PP resin.

The PP composition (I), a PP composition (I) obtained by blending the PP composition (I) with a linear PP resin.
The branching parameter of the PP composition obtained by blending the PP composition (II) with the linear PP resin is 0.9 or less, further 0.7 or less, and the gel fraction is 0.1%. Above, more preferably 1% or more from the viewpoint of improvement in transparency and workability.

In order to improve impact resistance without lowering the transparency of the PP composition (I), it has a refractive index substantially equal to that of linear polypropylene (hereinafter, also referred to as linear PP). A polyolefin rubber (hereinafter, also referred to as a specific polyolefin rubber) may be added.

The expression that the refractive indices are substantially equal means that the difference between the refractive indices is 0.02 or less, preferably 0.01 or less, and more preferably 0.005 or less. The refractive index may be measured or measured, for example, in Polymer Handbook 3rd Edition (John Wiley and Sons, 198).
9) and the like. The refractive index of the copolymer is a value calculated in proportion to the weight fraction of each monomer (the value of the monomer constituting the copolymer). The weighted average of the refractive index of the homopolymer and the weight fraction of the monomer is used.

The specific refractive index of each resin is determined from the above-mentioned Polymer Handbook and measured values: linear PP; 1.503 low-density polyethylene; 1.51 polyisobutene (polyisobutylene, polybutene);
1.505 to 1.51 butyl rubber; 1.508 polystyrene; 1.59 to 1.592 ethylene-propylene rubber; 1.4748 to 1.48 ethylene-butylene rubber; 1.457 to 1.47 (actual value) .

Specific examples of the specific polyolefin rubber include liquid polybutene (for example, Nisseki Polybutene HV-15, HV-300, manufactured by Nippon Petrochemical Co., Ltd.).
HV-3000 etc.) and crumb-like polybutene (for example, Tetrax 3T, 5T, 6T manufactured by Nippon Petrochemical Co., Ltd.)
Polyisobutylene (for example, Vistanex LM-MS, MML-80, manufactured by Exxon Chemical Co., Ltd.)
Liquid butyl rubber (for example, Karen 800 and Karen 130 manufactured by Exxon Chemical Co., Ltd.) among butyl rubbers composed of isobutylene and a small amount of isoprene.
0) or crumb-shaped butyl rubber (for example, butyl-065, butyl-268, butyl-butyl rubber manufactured by Nippon Synthetic Rubber Co., Ltd.).
365, Exxon butyl 06 manufactured by Exxon Chemical Co., Ltd.
5, 165, 077, 007); hydride of a random copolymer composed of an aromatic vinyl monomer and a diene monomer (for example, Dynallon 191 manufactured by Nippon Synthetic Rubber Co., Ltd.)
OH); a hydride of a block copolymer composed of an aromatic vinyl monomer and a diene monomer (eg, styrene-
Butadiene triblock copolymer or diblock copolymer hydride); Styrene-ethylene-butylene-styrene block copolymer (eg, Shellton Kraton G1650, G1652, G1726X, etc.); Styrene-isoprene-based Hydrogenated triblock copolymer or diblock copolymer; styrene-ethylene-propylene-styrene copolymer (for example,
Hydrogenated styrene-vinylated isoprene-styrene block copolymer (for example, HVS-3 manufactured by Kuraray Co., Ltd.);
Propylene-α olefin copolymer (for example, Tuffmer XR106L manufactured by Mitsui Petrochemical Industry Co., Ltd.) and the like.

The amount of the specific polyolefin rubber used is 10 to 90%, preferably 10 to 70%, particularly 10 to 50%, in terms of balance between transparency, workability, impact resistance and rigidity. Is preferred. In particular, those having a polyolefin-based rubber content of more than 50% have a linear PP content.
To the linear PP resin,
It can be used as a masterbatch of a modifier for improving impact resistance. Manufacturing a masterbatch is advantageous in terms of process and cost.

The above-mentioned specific polyolefin rubber is added at the time of producing the PP composition (I).
It may be performed when crosslinking a propylene-based resin (silylated PP-based resin) obtained by graft-copolymerizing a silyl group-containing monomer or when crosslinking a linear PP-based resin, a divinyl aromatic monomer, and a radical polymerization initiator. Good.

In particular, when a specific polyolefin rubber is added at the time of the above reaction, it is preferable because it can be easily dispersed.

When a specific polyolefin rubber is added during the reaction, when a silylated PP resin is used, the specific polyolefin rubber and the silylated PP resin are first melted and kneaded sufficiently. Crosslinking is preferred because it facilitates dispersion.

As described above, a modified propylene resin composition (hereinafter, also referred to as a modified PP composition) which is a PP composition (I) containing a specific polyolefin rubber (II)
I) is manufactured.

The obtained modified PP composition (III) is PP
The impact resistance is further improved in addition to the improvement of transparency and processability which are the characteristics of the system composition (I). Since a polyolefin rubber having the same refractive index as that of the linear PP resin is used, transparency is not impaired.

The modified PP composition (IV) in which the impact resistance of the PP composition (II) is improved may be produced by blending the PP composition (II) with a specific polyolefin rubber. . In this case, the blending ratio is 1 to 50%, more preferably 2 to 25%, of the specific polyolefin rubber based on the total amount of the PP composition (II) and the specific polyolefin rubber, and the transparency, It is preferable from the viewpoints of workability, impact resistance and rigidity.

The modified PP composition (III) or the modified PP composition (IV) of the present invention comprising the specific polyolefin rubber and the PP composition (I) or the PP composition (II). Can also be used as a modifier for a linear PP-based resin. Since the modified PP composition (III) or (IV) has excellent transparency, processability, impact resistance, etc., modification of the transparency, processability, impact resistance, etc. of the linear PP resin is performed. It can be used as an agent. Also, the modified P
P-based composition (III) or (IV) is replaced with PP-based composition (I)
Alternatively, it can be used for improving the impact resistance of (II), and in this case, good transparency and workability are maintained even if mixed at an arbitrary ratio.

As described above, the PP composition (I), the PP composition (II), and the modified PP composition (II) of the present invention
I) The modified PP composition (IV) may further include, if necessary, an antioxidant, a metal deactivator, a phosphorus-based processing stabilizer, and an ultraviolet absorber as long as the effects of the present invention are not impaired. Using additives such as UV stabilizers, fluorescent brighteners, stabilizers such as metal soaps, chain transfer agents, lubricants, plasticizers, fillers, reinforcing materials, pigments, dyes, flame retardants, antistatic agents Is also good.

An apparatus (a silyl group-containing monomer, a radical polymerization initiator and a linear polymerization initiator) used for branching and crosslinking the mixture of the linear PP resin or the olefin rubber and the silylated PP resin in a molten state. Including an apparatus used when graft copolymerizing a PP resin in a molten state), when branching and crosslinking a divinyl aromatic monomer, a radical polymerization initiator, and a linear PP resin in a molten state Apparatuses used include kneaders such as rolls, co-kneaders, Banbury mixers, Brabenders, single-screw extruders, twin-screw extruders, etc. A vertical stirrer such as a helical ribbon stirrer may be used. Of these, extruders are particularly preferred from the viewpoint of productivity.

The temperature of the apparatus is preferably from 130 to 400 ° C. from the viewpoint that the linear PP resin melts and does not thermally decompose. The time is generally 1 to 60 minutes.

The PP composition (I), PP composition (II), modified PP composition (III), and modified PP composition (IV) of the present invention have excellent transparency and processability. When a specific olefin-based rubber is contained, even better impact resistance and the like are exhibited, so that a molding method that is difficult when a conventional propylene-based resin composition is used is also used. Useful molded articles can be produced by various molding methods including the above.

Examples of the molding method used for the PP composition (I), the PP composition (II), the modified PP composition (III), and the modified PP composition (IV) of the present invention include: Examples include an extrusion molding method, a calender molding method, a vacuum molding method, a thermoforming method such as a pressure molding method, an injection molding method, a blow molding method, and a foam molding method.

For example, the PP composition (I), P
P-based composition (II), modified PP-based composition (III), modified P
By extruding or calendering the P-based composition (IV), a film or sheet-like molded article can be obtained. Further to the film or sheet-like molded body,
By performing thermoforming at a suitable temperature, a thermoformed body can be obtained. In addition, an injection molded article or a blow molded article can be obtained by injection molding or blow molding the composition. Further, a foam can be obtained by adding a foaming agent to the composition and subjecting the composition to foam molding using an autoclave or an extruder.

[0062]

Next, the present invention will be described based on examples and comparative examples, but the present invention is not limited to these examples.

The twin-screw extruder used in the following Examples and Comparative Examples was Labotex (3) manufactured by Japan Steel Works, Ltd.
2 mmφ, L / D = 25.5).

Table 1 shows main resins and the like used in Examples and Comparative Examples.

[0065]

[Table 1]

The silylated PP (2) in Table 1 is a homopolypropylene powder (J3 manufactured by Mitsui Petrochemical Industries, Ltd.).
00P, MI 1.4) 100 parts and methacryloxypropyltrimethoxysilane (A manufactured by Nippon Unicar Co., Ltd.)
174) 3.5 parts of polymerization initiator benzoyl peroxide (Nivar BW manufactured by NOF Corporation) 0.5 part
It is obtained by melt graft polymerization with a twin screw extruder at 00 ° C.

The evaluation methods used in the examples and comparative examples are shown below.

(Gel Fraction) The weighed pellet was 10 μm
After dissolving in xylene having a 600-fold weight at 130 ° C. for 6 hours, the gel content remaining in the wire mesh bag was vacuum-dried at 50 ° C. for 8 hours, and the weight was measured. The ratio to the initial pellet weight was determined.

(Branching parameter) High-temperature GPC of hot xylene-soluble matter (polyolefin-based rubber is excluded as normal-temperature xylene-soluble matter) of the PP composition or the modified PP composition.
In the measurement, multi-director GPC software Ver3.00 (manufactured by Nippon Waters Limited) was used to calculate from the chromatogram of the RI detector and the chromatogram of a viscometer directly connected to GPC, and the value in the weight average molecular weight was adopted.

(Transparency) Using a 1 mm thick test piece,
The total light transmittance (T%) and the turbidity (Haze%) were measured according to STM-D1003.

(Izod impact strength) ASTM-D25
6, 23 ° C and -20 ° C according to ASTM-D790
Was measured for impact strength.

(Odor during measurement of sagging and sagging) A clamp having an opening of 180 mm × 180 mm and 200 mm ×
200mm, 1.0mm thick sheet is fixed, 250mm
Hold in oven at ℃ for 3 minutes and draw down (mm)
Was measured. Those with a small value of sag have high sag resistance and excellent workability.

During the measurement of sag, it was examined whether there was a problem of odor generated when a conventional low molecular weight organic nucleating agent was used.

Example 1 100 parts of silylated PP (1) and 0.05 part of dibutyltin dilaurate were supplied from a feeder, and 20 parts of water were supplied from a side feeder to a twin-screw extruder set at 200 ° C. After the branching and cross-linking reaction, the strand is pelletized to obtain a PP-based resin-containing composition (PP-based composition I-) having a diameter of about 5 mm and a length of about 5 mm.
1) A pellet was obtained (the pelletizing step and the shape of the pellet to be produced are the same in the following Examples and Comparative Examples, and the description is omitted below).

Using the pellets obtained, the gel fraction and branching parameters were determined. The obtained pellets were roll-kneaded at 200 ° C. to produce a roll sheet.
0 ° C, 30 kgf / cm ² , 10 minutes, 20 ° C, 50 kg
The test pieces and sheets used in each test method were prepared by press molding under conditions of f / cm ² and 5 minutes, and evaluated. Table 2 shows the results.

Example 2 75 parts of silylated PP (1), 25 parts of butyl rubber and 0.05 part of dibutyltin dilaurate were fed from a feeder.
20 parts of water is supplied from a side feeder to a twin-screw extruder set at 200 ° C., and branched and cross-linked in a molten state to form a modified PP composition (modified PP composition III-1). The pellet was obtained.

Evaluation was performed in the same manner as in Example 1 using the obtained pellets. Table 2 shows the results.

Example 3 50 parts of silylated PP (1), 50 parts of butyl rubber and 0.05 part of dibutyltin dilaurate were fed from a feeder.
In addition, 20 parts of water is supplied from a side feeder to a twin-screw extruder set at 200 ° C., and branched and cross-linked in a molten state to form a modified PP composition (modified PP composition III-2). The pellet was obtained.

Evaluation was performed in the same manner as in Example 1 using the obtained pellets. Table 2 shows the results.

Example 4 25 parts of silylated PP (1), 75 parts of butyl rubber and 0.05 part of dibutyltin dilaurate were fed from a feeder, and 20 parts of water from a side feeder to a twin-screw extruder set at 200 ° C. Then, the modified PP-based composition (modified PP)
System composition III-3) A pellet was obtained.

Using the obtained pellets, evaluation was made in the same manner as in Example 1. Table 2 shows the results.

Example 5 75 parts of silylated PP (1), 25 parts of SEBS and 0.05 parts of dibutyltin dilaurate were fed from a feeder.
In addition, 20 parts of water is supplied from a side feeder to a twin-screw extruder set at 200 ° C., and branched and cross-linked in a molten state to form a modified PP resin composition (modified PP).
System composition III-4) Pellets were obtained.

Evaluation was performed in the same manner as in Example 1 using the obtained pellets. Table 2 shows the results.

Example 6 75 parts of silylated PP (1), 25 parts of SEPS and 0.05 part of dibutyltin dilaurate were fed from a feeder.
In addition, 20 parts of water is supplied from a side feeder to a twin-screw extruder set at 200 ° C., and branched and cross-linked in a molten state to form a modified PP resin composition (modified PP).
System composition III-5) Pellets were obtained.

Evaluation was performed in the same manner as in Example 1 using the obtained pellets. Table 2 shows the results. In addition, NB in Table 1 shows that it did not break.

Example 7 50 parts of PP (2) and 50 parts of silylated PP (2) were fed from a feeder to a twin-screw extruder set at 200 ° C.
By kneading in a molten state, PP-based composition (PP-based composition II-1) pellets were obtained.

The obtained pellets were evaluated in the same manner as in Example 1. Table 2 shows the results.

Example 8 80 parts of PP (2) and 20 parts of silylated PP (2) were fed from a feeder to a twin-screw extruder set at 200 ° C.
By kneading in a molten state, PP-based composition (PP-based composition II-2) pellets were obtained.

Evaluation was performed in the same manner as in Example 1 using the obtained pellets. Table 2 shows the results.

Example 9 80 parts of PP (2), 20 parts of silylated PP (2) and S
EBS 10 parts were set to 200 ° C from the feeder 2
The modified PP-based resin composition (modified PP-based composition IV-1) pellets was obtained by supplying the mixture to a screw extruder and kneading in a molten state.

Using the obtained pellets, evaluation was made in the same manner as in Example 1. Table 2 shows the results.

Example 10 90 parts of PP (2) and 10 parts of silylated PP (2) were fed from a feeder to a twin-screw extruder set at 200 ° C.
By kneading in a molten state, PP-based composition (PP-based composition II-3) pellets were obtained.

Using the obtained pellets, evaluation was made in the same manner as in Example 1. Table 2 shows the results.

Example 11 95 parts of PP (2) and 5 parts of silylated PP (2) were fed from a feeder to a twin-screw extruder set at 200 ° C. and kneaded in a molten state to obtain PP-based composition pellets. I got

Using the obtained pellets, evaluation was made in the same manner as in Example 1. Table 2 shows the results.

Example 12 50 parts of random PP (1) and silylated PP (2) 5
0 parts was supplied from a feeder to a twin-screw extruder set at 200 ° C. and kneaded in a molten state to obtain PP-based composition (PP-based composition II-4) pellets.

Using the obtained pellets, evaluation was made in the same manner as in Example 1. Table 2 shows the results.

[0098]

[Table 2]

Example 13 100 parts of PP (1) and 20 parts of the PP composition I-1 obtained in Example 1 were fed from a feeder to a twin-screw extruder set at 200 ° C. and kneaded in a molten state. By doing so, a PP-based composition II-5 pellet was obtained.

Using the obtained pellets, evaluation was made in the same manner as in Example 1. Table 3 shows the results.

Example 14 100 parts of PP (1) and the modified PP obtained in Example 2
10 parts of the system composition III-1 was fed from a feeder to a twin-screw extruder set at 200 ° C., and kneaded in a molten state to obtain a modified PP resin composition IV-2 pellet.

The obtained pellets were evaluated in the same manner as in Example 1. Table 3 shows the results.

Example 15 100 parts of PP (1) and the modified PP obtained in Example 2
Twenty parts of the system composition III-1 was fed from a feeder to a twin-screw extruder set at 200 ° C. and kneaded in a molten state to obtain a modified PP system composition IV-3 pellet.

Evaluation was performed in the same manner as in Example 1 using the obtained pellets. Table 3 shows the results.

Example 16 100 parts of PP (1) and the modified PP obtained in Example 2
80 parts of the system composition III-1 was fed from a feeder to a twin-screw extruder set at 200 ° C. and kneaded in a molten state to obtain modified PP composition IV-4 pellets.

Evaluation was performed in the same manner as in Example 1 using the obtained pellets. Table 3 shows the results.

Example 17 100 parts of PP (1), 20 parts of the modified PP composition III-1 obtained in Example 2, and 10 parts of butyl rubber were fed from a feeder to a twin-screw extruder set at 200 ° C. Then, the modified PP-based composition IV-5 pellets were obtained by kneading in a molten state.

Evaluation was performed in the same manner as in Example 1 using the obtained pellets. Table 3 shows the results.

Example 18 100 parts of PP (1), 20 parts of the modified PP composition III-1 obtained in Example 2, and 80 parts of butyl rubber were fed from a feeder to a twin-screw extruder set at 200 ° C. Then, by kneading in a molten state, a modified PP-based composition IV-6 pellet was obtained.

Evaluation was performed in the same manner as in Example 1 using the obtained pellets. Table 3 shows the results.

Example 19 100 parts of PP (1) and the modified PP obtained in Example 3
Twenty parts of the system composition III-2 was supplied from a feeder to a twin-screw extruder set at 200 ° C., and kneaded in a molten state to obtain modified PP composition IV-7 pellets.

Evaluation was performed in the same manner as in Example 1 using the obtained pellets. Table 3 shows the results.

Example 20 100 parts of PP (1) and the modified PP obtained in Example 4
Twenty parts of the system composition III-3 was fed from a feeder to a twin-screw extruder set at 200 ° C, and kneaded in a molten state to obtain a modified PP system composition IV-8 pellet.

Evaluation was performed in the same manner as in Example 1 using the obtained pellets. Table 3 shows the results.

Example 21 100 parts of PP (1) and the modified PP obtained in Example 5
Twenty parts of the system composition III-4 was supplied from a feeder to a twin-screw extruder set at 200 ° C, and kneaded in a molten state to obtain a modified PP system composition IV-9 pellet.

Evaluation was performed in the same manner as in Example 1 using the obtained pellets. Table 3 shows the results.

Example 22 100 parts of PP (1) and the modified PP obtained in Example 6
Twenty parts of the system composition III-5 was fed from a feeder to a twin-screw extruder set at 200 ° C., and kneaded in a molten state to obtain a modified PP composition IV-10 pellet.

Evaluation was performed in the same manner as in Example 1 using the obtained pellets. Table 3 shows the results.

Example 23 100 parts of PP (2) and 20 parts of the PP-based composition II-1 obtained in Example 7 were fed from a feeder to a twin-screw extruder set at 200 ° C. and melted. By kneading, a PP-based composition II-6 pellet was obtained.

Evaluation was performed in the same manner as in Example 1 using the obtained pellets. Table 3 shows the results.

Example 24 100 parts of PP (2) and 20 parts of the PP composition II-4 obtained in Example 12 were fed from a feeder to a twin-screw extruder set at 200 ° C., and kneaded in a molten state. By doing so, a PP-based resin composition II-7 pellet was obtained.

Using the obtained pellets, evaluation was made in the same manner as in Example 1. Table 3 shows the results.

Example 25 100 parts of random PP (2) and 20 parts of the modified PP-based composition III-2 obtained in Example 3 were placed in a feeder through a feeder.
The modified PP-based composition IV-11 pellets were obtained by supplying the mixture to a twin-screw extruder set at 00 ° C and kneading in a molten state.

Evaluation was performed in the same manner as in Example 1 using the obtained pellets. Table 3 shows the results.

[0125]

[Table 3]

Example 26 100 parts of PP (1) and divinylbenzene (DVB)
/Xylene=0.75 parts / 20 parts of a mixture of di-t-butyl peroxide / xylene = 0.
Add 25 parts / 3.5 parts of the mixture from the side feeder to 20 parts.
The mixture was fed to a twin-screw extruder set at 0 ° C. and reacted in a molten state to obtain a PP-based composition I-2 pellet.

Evaluation was performed in the same manner as in Example 1 using the obtained pellets. The branch parameters were also evaluated. Table 4 shows the results.

Example 27 A mixture of 100 parts of PP (1) and 0.75 parts / 40 parts of divinylbenzene / xylene was fed from a feeder, and di-t-butyl peroxide / xylene was 0.2%.
5 parts / 7 parts of the mixture was fed from a side feeder to 200 ° C.
Was supplied to a twin-screw extruder and reacted in a molten state to obtain PP-based composition I-3 pellets.

Using the obtained pellets, evaluation was made in the same manner as in Example 26. Table 4 shows the results.

Example 28 A mixture of 100 parts of PP (1) and 1.5 parts / 40 parts of divinylbenzene / xylene was fed from a feeder.
Di-t-butyl peroxide / xylene = 0.5 part /
7 parts of the mixture was supplied from a side feeder to a twin-screw extruder set at 200 ° C. and reacted in a molten state to obtain PP-based composition I-4 pellets.

The obtained pellets were evaluated in the same manner as in Example 26. Table 4 shows the results.

Example 29 A mixture of 50 parts of PP (1), 50 parts of butyl rubber and 0.75 parts / 20 parts of divinylbenzene / xylene was fed from a feeder, and di-t-butyl peroxide / xylene = 0.25 parts. Parts / 3.5 parts of the mixture is supplied from a side feeder to a twin-screw extruder set at 200 ° C. and reacted in a molten state, whereby the modified PP-based composition III
-6 pellets were obtained.

The obtained pellets were evaluated in the same manner as in Example 26. Table 4 shows the results.

Example 30 50 parts of the PP composition I-2 and 50 parts of butyl rubber obtained in Example 26 were fed from a feeder to a twin-screw extruder set at 200 ° C., and kneaded in a molten state. Thus, a modified PP-based composition III-7 pellet was obtained.

The obtained pellets were evaluated in the same manner as in Example 26. Table 4 shows the results.

[0136]

[Table 4]

Comparative Example 1 Evaluation was made in the same manner as in Example 1 using only PP (1). Table 5 shows the results.

Comparative Examples 2 to 5 PP (1) was added to butyl rubber, polyolefin rubber, L
DPE, an organic nucleating agent, etc. were added, pelletized in the same manner as in Example 1, and evaluated. Table 5 shows the results.

[0139]

[Table 5]

The PP composition (I) of the present invention and the PP composition (II) containing the same have improved transparency and processability, and the modified PP composition of the present invention (II)
It can be seen that I) and the modified PP composition (IV) containing it have improved transparency, workability and impact resistance. In particular, with respect to transparency, it can be seen that a molded article having a transparency equal to or higher than that of a system obtained by adding a conventional low molecular weight organic nucleating agent can be obtained. Regarding workability,
It can be seen that a molded article having processability equal to or higher than that of the system to which the conventional low-density polyethylene is added can be obtained. It can be seen that there is no problem of odor during processing generated by the conventional low molecular weight organic nucleating agent. Furthermore, regarding impact resistance,
It can be seen that a molded article having an impact resistance close to that of a system to which a conventional polyolefin rubber is added can be obtained.

[0141]

Industrial Applicability The PP composition (I) of the present invention and the PP composition (II) containing the composition have both high transparency and workability, and give a molded article which is hard to bleed out. Further, the modified PP-based composition (III) of the present invention and the modified PP-based composition (IV) containing the composition have high transparency,
Provides a molded product that has both processability and impact resistance and is less likely to bleed out. These molded articles retain the characteristics of the propylene-based resin, such as rigidity, heat resistance, and chemical resistance, as they are.

Claims (11)

[Claims] 1. A branching parameter of 0.9 to 0.1 obtained by a branching and crosslinking reaction of a linear propylene resin.
A propylene resin composition (I) comprising 10 to 99.99% by weight of a branched propylene resin and 0.01 to 90% by weight of a crosslinked propylene resin. 2. A linear propylene resin of 99 to 1% by weight.
And a propylene-based resin composition (II) comprising 1 to 99% by weight of the propylene-based resin composition (I). 3. A propylene resin composition (I) 90-1.
0% by weight and 10 to 90% by weight of a polyolefin rubber having a refractive index substantially equal to that of linear polypropylene
A modified propylene resin composition (III) comprising: 4. A propylene-based resin composition (II) 99-5.
A modified propylene-based resin composition (IV) comprising 1 to 50% by weight of a polyolefin rubber having a refractive index substantially equal to 0% by weight and a linear polypropylene. 5. The branching and crosslinking reaction of a linear propylene-based resin is a branching and crosslinking reaction of a silylated propylene-based resin obtained by graft copolymerizing a linear propylene-based resin with a silyl group-containing monomer. The propylene-based resin composition (I) described above. 6. The propylene resin according to claim 1, wherein the branching and crosslinking reaction of the linear propylene resin is a branching and crosslinking reaction of the linear propylene resin, a divinyl aromatic monomer and a radical polymerization initiator. Composition (I). 7. The propylene-based resin according to claim 1, wherein the silylated propylene-based resin obtained by graft-copolymerizing a silyl group-containing monomer to a linear propylene-based resin is melt-kneaded and subjected to a branching and crosslinking reaction. Production method of resin composition (I). 8. The propylene resin composition (I) according to claim 1, wherein the linear propylene resin, the divinyl aromatic monomer and the radical polymerization initiator are subjected to a branching and crosslinking reaction in a melt-kneaded state. ) Manufacturing method. 9. A branching and cross-linking reaction in a melt-kneaded state of a linear propylene resin and a silylated propylene resin obtained by graft copolymerizing a silyl group-containing monomer with the linear propylene resin. Claim 2
The method for producing the propylene-based resin composition (II) described above. 10. A silylated propylene resin obtained by graft copolymerizing a silyl group-containing monomer to a linear propylene resin and a polyolefin rubber having a refractive index substantially equal to that of the linear polypropylene are melt-kneaded. The method for producing a modified propylene-based resin composition (III) according to claim 3, wherein a branching and crosslinking reaction of the silylated propylene-based resin is performed. 11. A linear propylene resin, a silylated propylene resin obtained by graft copolymerizing a silyl group-containing monomer to the linear propylene resin, and a polyolefin resin having a refractive index substantially equal to that of the linear polypropylene. 5. The method for producing a modified propylene resin composition (IV) according to claim 4, wherein the rubber is subjected to a branching and crosslinking reaction of the silylated propylene resin in a melt-kneaded state.