JPS5896639A - Polyolefin resin composition containing surface treatment reinforcing agent - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention provides a polyolefin blended with a surface-treated reinforcing material, which has significantly improved properties such as mechanical performance, surface appearance, and moldability by filling a 19 olefin with a reactively coated reinforcing material. This relates to resin composition constraints.

In recent years, general-purpose engineering resins such as nylon, ABS (acrylonitrile/butadiene/styrene copolymer), and -recarbonate I-lyacetal have been replacing conventionally used metals, wood, and ceramics.

Sara・Ko,〆Polyfins such as polyethylene and polypropylene have improved heat deformation temperature, rigidity, hardness, etc.
Research has been carried out on a wider range of applications and developments.

Many of the researches on improving these polyolefins include filling them with reinforced fibers or fine inorganic reinforcing materials to improve their rigidity, heat distortion temperature, etc.

Is this inorganic reinforcement material due to its low price? The cost/performance position of squirrel resin is superior to other materials, and many applications are beginning to be developed.

However, when the reinforcing material of Nire et al. is added to polyolefin 1ζ, the rigidity etc. are generally improved, but the elongation is significantly lowered and the impact strength is also significantly lowered.

Furthermore, the composition of the energized polyolefin and the reinforcing material is formed by melt-kneading, but if a reinforcing material with a fine particle size is used, the dispersion state becomes poor, which causes poor appearance and impact strength. Furthermore, some highly filled compositions cannot be melted and kneaded.

In order to improve these defects, many proposals have been made to improve the impact strength by applying various surface treatments to the surface of the life-reinforcing material.

For example, it is known to treat the surface of a reinforcing material with a silane coupling agent or a titanium-based coupling agent, but the reinforcing effect is low.

It is also known to coat the surface of reinforcing materials with surfactants, higher fatty acids, and their metals, or to add them during melt-kneading, but these substances are generally low molecular weight substances. Because of this, the oJffi phenomenon occurs and the rigidity is lowered.
There is a problem with this. If gold ri4@, which is a higher fatty acid, is added, problems such as bleeding on the surface of the hood and ζ will impair the appearance and corrosion of the mold will occur during molding.

There is a need to develop a resin composite that solves these problems and has high physical properties and high moldability.

If the reinforcing material and the resin have good compatibility and a strong chemical bond exists between them, the dispersibility of the reinforcing material will be good (F)
It is believed that various mechanical properties are improved. For example, Japanese Patent Publication No. 66-18080 proposes a method of reaction-coating the surface of powder with an acrylic acid (or methacrylic acid) copolymer having double bond residues.

In this proposal, when applying this to 19T reflexine, it is recommended to add 2 this peroxide to the 19T olefin in order to add the double bond in this copolymer to 19T refin, and bond with the polyolefin. However, problems such as decomposition or crosslinking of -lyolefin by peroxide cannot be avoided.

In addition, there are no known methods to increase compatibility with polyolefins, and what is more, it is highly polar, such as acrylic acid (or methacrylic acid) copolymers. 97- and the polyolefin rather inhibit the dispersion of the reinforcing material powder, which exhibits affinity.

It is expected that introducing a chemical bond between the reinforcing material and the polyolefin resin will improve mechanical properties, but it is not known that introducing an open ζ chemical bond with the reinforcing material while maintaining compatibility with the polyolefin resin. Until now, complete bonding between reinforcing materials and polyolefin resins could not be expected in systems with good dispersion.

The present inventors completed the present invention by conducting intensive research to completely disperse the reinforcing material into the polyolefin and at the same time perfecting the bond between the surface of the reinforcing material and 19<refin 5IBH.・It has come to this. That is, the present invention provides (1) a substance having a weight average molecular weight to that is soluble in n-hexane and contains 5 mol% or more of methacrylic acid or acrylic acid;
A polyolefin resin composition containing a reinforcing material whose surface is reactively coated with a copolymer of methacrylic acid or acrylic acid of 00 or more.

(2) As a component of a copolymer of methacrylic acid or acrylic acid, the side chain has a length of 8 or more carbon atoms and has a length of D 7 tk.
The polyolefin resin composition according to (1), characterized in that an acrylic ester having a compound is used.

(8) As a methacrylic acid copolymer, it has 6 to 40 mole% of methacrylic acid, 0 to 10 mole% of methyl methacrylate, and an alkyl group having a length of 8 or more carbon atoms in the side chain. The polyolefin resin composition according to (1), characterized in that a terpolymer having a composition of 60 to 90 mol% of acrylic acid ester is used.

(4) The polyolefin resin composition according to (1), characterized in that a basic inorganic reinforcing material that exhibits a neutralization reaction with methacrylic acid is used as the reinforcing material.

(6) The reinforcing material is made of liquid paraffin (specific gravity 0.855 f/-, g5C viscosity 1
The polyolefin resin composition according to (1), characterized in that the viscosity at 26C is 600 centimeters or more when mixed at 10 wt% with respect to 60 centimeters.

It has to do with fists.

Methacrylic acid (or acrylic acid) used in the present invention
It is essential that the copolymer be soluble in n-hexane. This condition defines the compatibility with the polyolefin, and when expressed more quantitatively, it is expressed by the viscosity of the liquid paraffin/talc dispersion.

That is, talc (particle size l~6μ) whose surface is coated with the methacrylic acid (or acrylic acid) copolymer of the present invention
) to liquid paraffin (ratio ff10.866f/j, 25
The viscosity at 25C is 500 centimeters (tut"
(abbreviated as ps) or below is desirable.

The carboxylic acid groups in the copolymers of the present invention contribute to an ethical bond with the reinforcing material. If there are bone ζ hydroxyl groups on the surface of the reinforcing material, hydrogen bonding can be detected, and if a non-metallic material such as a metal compound is used as the reinforcing material, the surface reaction coating using the methacrylic acid copolymer can be observed in the infrared absorption spectrum. The difference spectrum between the inorganic material and the uncoated material shows the absorption peak that occurs when carboxylic acid reacts, indicating the presence of loose chemical bonds.

The viscosity low F effect and chemical bonding strength obtained when a resin composition is obtained by melt-kneading the coating reinforcing material of the present invention and meliolefin alone or a blend of meliolefin and rubber are the same as those of the coating reinforcing material mentioned above. The purpose of Trix is to disperse the contents evenly, without creating agglomerates, and to make them chemically unified.

As a result, the composition O obtained by dispersing the coated reinforcing material of the present invention in a soot resin exhibits high mechanical properties, practical physical properties, and moldability.

Therefore, when coated with methacrylate or acid copolymer insoluble in n-hexane and mixed with 10% by weight of 260 Flow III halafine as a coating reinforcement material, the viscosity is 500 cpsQ.
- In the case of H, a composition having excellent mechanical properties and practical physical properties cannot be obtained.

The composition of the present invention dramatically improves mechanical properties such as impact resistance, tensile strength, and elongation. This means that the bond between the imported wood and the gliorefin was completely revealed, and the reinforcement
The n-hexane used in the composition of the present invention is estimated to have good dispersibility in the refractory and to avoid introducing defects into the composition due to aggregation of reinforcing materials.・It was only by using this soluble acrylic acid (or methacrylic acid) copolymer that it was possible to exhibit the advanced mechanical properties described in detail in the actual inversion. This improvement in folding strength was completely expected.
This is an effect of the present invention, and it is presumed that the main cause of this effect is the affinity with polyolefin shown in the Jl property to n-hexane. Rather than creating a chemically strong bond with the polyolefin via a double bond, it has the flexibility to deform in response to external forces with a loose bond similar to the strength of polyolefin and Van de Waals. It is thought that this is effective for bending strength, but the details are unknown.

The concentration of the methacrylic acid (or acrylic acid) component in the methacrylic acid (or acrylic acid) copolymer used in the present invention is in the range of 6 to 80%, preferably 10%.
The range is from 10 to 60% by mole, more preferably from 10 to 40% by mole.

If it is outside this range, sufficient bonding with the reinforcing material cannot be achieved.

A. Methacrylic acid (or methacrylic acid) used in the present invention
It is desirable that the weight average molecular weight of the copolymer is 10,900 or more; if the molecular weight is low, sufficient effects cannot be expected.

Any reinforcing material can be used in the present invention as long as it has a surface capable of reacting with carboxylic acid groups.

For example, carbonates, silicates, hydroxides or oxides of metals of Group 1 of the periodic law, or hydroxides of aluminum, such as calcium carbonate, magnesium carbonate, barium carbonate, zinc carbonate, etc. Carbonates, silicates such as calcium silicate, magnesium sulfate, low hydroxide,
Magnesium hydroxide, hydroxides such as ram, oxidizing power C lesium, magnesium oxide, beryllium oxide, zinc oxide, and other oxides can be used.

It can also be applied to fibrous reinforcing materials such as hemp and other sererose fibers.

Methacrylic acid (or acrylic acid) used in the present invention
It is essential that the copolymer is crJI@ in n-hexane, and is an acrylic acid (or methacrylic acid) ester having an alkyl chain with 8 or more carbon atoms in the wire-carrying side chain. It is desirable to use a copolymer of 9M acid (
Alternatively, examples of the methacrylic acid ester include acrylic acid-2-ethycehexyl, acrylic acid ester, acrylic acid ester, and acrylic acid stearyl ester.

When the co-wealth ratio is extremely different - this is a ternary combination using a third component such as methyl methacrylate! Using a combination analogy,
The solubility in n-hexane is increased, and the effects of the present invention can be further expressed.

The methods for producing methacrylic acid (or acrylic acid) copolymers are not limited to special costs, but include bulk polymerization, polymerization in an aqueous solution, polymerization in a solvent, and irradiation polymerization. Both methods are possible.

The amount of the methacrylic acid (or acrylic acid) copolymer used is preferably in the range of 0.1 to 20% based on the reinforcing material M, more preferably in the range of to-Qto%. .

Various methods can be employed to reactively coat the surface of the reinforcing material with the methacrylate (or acrylic acid) copolymer used in the present invention. 7 For example, a method in which a reinforcing material is added to and mixed with the solution of the above-mentioned methacrylic acid (or acrylic acid) copolymer while stirring, and at the same time as the coating reaction or after the coating reaction, saliva and solvent are removed and dried. There is. Alternatively, a method in which the reinforcing material and the copolymer of the present invention are homogeneously mixed and then a copolymerization reaction is carried out is also a preferred method since coating can be performed simultaneously with polymerization.

The coating reinforcement material obtained by the distribution method is f! rli〆Refin can be used alone or in a blend of polyolefin and rubber.

Examples of the polystyrene resin used in the present invention include polyethylene (high-density, low-density, crystalline ethylene-propylene blocks combined into one, polybutene, poly-4-methylpentene-1, etc.). Rubbers that can be used with the present invention include natural rubber, inobrene, butadiene rubber, SB rubber, ethylene-propylene rubber, and ethylene-butene copolymer.

These 7 trix materials and the coating reinforcing material of the present invention can be blended by various conventionally known melt intermixing methods.

The amount of the coating reinforcing material of the present invention added to the finishing resin is relatively high, and it is possible to fill the resin to almost full capacity.

The concentration of the reinforcing material should be selected depending on the required performance of the application. Lyolefin resin 20-80% by weight
・Coated reinforcement material 80-20! It is possible within a range of 3%.

The compounded composition of the present invention may contain stabilizers, ultraviolet absorbers, etc. as required. It may contain lubricants, pigments, flame retardants, antistatic agents, binders, blowing agents, solvents and other additives.

Hereinafter, in order to more specifically explain the features of the present invention, the present invention will be explained in more detail using Examples and Reference Examples.However, the scope of the present invention will be limited by the following Examples and Reference Examples. Of course, this is not something that can be done. In addition, parts and % used in Examples and Reference Examples are parts by weight, respectively.
Weight%.

Examples 1-1 to 8 Acrylic I! I! 2-ethyl, abbreviated as 2-EHA 1,
19.6F (referred to as component A) and methyl methacrylic acid (referred to as component A)
Melt 1.25f of MMA (abbreviated as component B), 1.6f of metacrylic acid (abbreviated as MAA and call component C) in 100% of water, and melt laurot-t-quinide as a medium-ζ. Polymerization was carried out at 60 to 65C. Poly 7- was separated by heat treatment, loaded, and dried. The obtained copolymer was soluble in n-hexane. Under similar conditions, Aku91 was used as the A component.
A copolymer was produced using lauric acid (abbreviated as LA) and acrylic acid stearic acid+ (abbreviated as SA).

Comparative Examples 1-1 to 6 Methyl acrylate (abbreviated as MA) and glycidyl methacrylate LG as component A under the same conditions as Example 1
A copolymer was produced using hydroxyethyl methacrylate (abbreviated as MA) and hydroxyethyl methacrylate (abbreviated as HEMA).

In addition, a system that uses MA as the A component and does not contain the B component, A
A copolymer was produced in a system containing no components.

The n-
The solubility in hexane and the copolymer's solubility in hexane or copolymer were as shown in the Examples or Comparative Examples below.
Rem: manufactured by Hayashi Kasei (average particle diameter 8.9μ)) was mixed with liquid paraffin at a concentration of 10%, and the viscosity at 26C was measured using a B-type viscometer.

The results are shown in Table 1.

Examples 2-1 to 8 Copolymer 10F obtained in Example 1-1 was dissolved in n-hexane 12009, and this solution and talc tooor were mixed and stirred at room temperature for 10 minutes in a crusher to make a paste. I looked down. After removing the solvent using a vacuum dryer, dry with hot air at 1800 ℃ for 2 hours. Thereafter, it was pulverized using a small pulverizer to obtain a reaction-coated filler.

This 4@ and M, 1.8.0 ethylene-propylene block copolymer (hereinafter referred to as Doblock PP) were mixed in a tabletop kneader (PBV-08 manufactured by Irie Shokai Co., Ltd.) in the proportions shown in Table 2.
-H type) at a resin temperature of 210 C and melt-kneaded 5 molecules i11 and formed into a sheet with a roll.

The resulting resin composition was compression molded, and its physical properties were measured according to ASTM and JIS standards. The results obtained are shown in Table 2.

Comparative Examples 2-1 to 2-8 The block PP used in Examples and uncoated talc were melt mixed and compression molded in the same manner as in Example 2, and the physical properties were measured. The results obtained are shown in Table 2.

Comparative Examples 2-4 to 8 The copolymer obtained in Comparative Example 1 was used as a solvent at °Cchloropho! The talc surface was treated using Rem. A resin composition was obtained using the talc and block PP in the filling amounts shown in Table 2 in the same manner as in Example 2.

The results of physical property measurements are shown in Table 2.

Tensile strength: Unit t7 (ASTMD-688) Elongation 2 units % (ASTMD-688) Izotsu technique - Strength 2 unit image/tan/100 notches (ASTMD-256) 1 fold strength 2 units times (JIS P8116) Example 8-1 to 8 Using the copolymer obtained in Example 1, reaction coating was filled in the same manner as in Example 1 using finely divided cesium carbonate (average particle m0.15μ, Brilliant ■ manufactured by Shiraishi Calcium) as a filler. obtained the drug.

Using this reactive coating agent, mixed extrusion was carried out with block PP in a 25M8-screw extruder at the compounding ratio shown in Table 8.
I created a field of μ seasons and measured the number of lumps using a universal projector. In addition, the scratch load (2) during kneading and extrusion was measured. The eyelids are shown in Table 8.

Comparative Examples 8-1 to 8 Using the finely powdered calcium carbonate (uncoated) used in Example 8, films were prepared by extrusion at °C in the same manner as in Example 8.

The number of holes in the film and the screw load during extrusion were measured and the results are shown in Table 8.1ζ.

Table 8 (size of about 90.111!1 pieces per ty) Example 4 Same as Example 2-2 using the copolymer obtained in Example 1-2.1-8. #Ii skin composition was prepared by reaction coating or kneading Rref and block PP using the method described in the following.

This resin composition is compression molded and conforms to ASTM standards and JI standards.
Physical properties were measured according to S standard. The results obtained are shown in Table 4.

Table 4 Reference example

Claims (1)

[Scope of Claims] (1) Weight average molecular weight to which is soluble in n-hexane and contains methacrylic acid or acrylic acid at 7M% or more
A polyolefin resin composition containing a reinforcing material whose surface is reaction-coated with a copolymer of acid or acrylic acid. (2) Claim 1 characterized by a fist using an acrylic acid ester having an alkyl heavy chain having a side chain cloudy ζ carbon number of 8 or more as one component of a copolymer of methacrylic acid or acrylic acid. The meliolefin resin composition described. (8) Methacrylic acid 6 as methacrylic acid copolymer
~40 mol%, ~0~10 mol% of methi methacrylate, and Φ60~90 mol% of acrylic acid ester having a 1-alkyl chain with a length of 8 or more carbon atoms in the side chain. Patent rust search range characterized by using! The polyolefin wood composition according to item 1. (4) The claimed finic acid 1-fat composition, characterized in that a basic inorganic reinforcing material that exhibits a neutralization reaction with methacrylic acid is used as a reinforcing material. (5) The reinforcing material is a copolymer of methacrylic acid or acrylic acid coated on the surface of tallylin (particle size 1 to 5μ), and then liquid paraffin (specific gravity 0.8561/ad26C).
The polyolefin resin composition according to claim 1, characterized in that the viscosity at 26C is 600 centimeter UP when mixed at 10 wt% with respect to a viscosity of 160 centimeter.