JPH02173020A - Production of crystalline styrene block copolymer resin - Google Patents

Abstract

PURPOSE:To obtain a crystalline resin having improved compatibility with wax and sufficient toughness and being utilizable as a resin modifier by grafting a specified resin onto a saturated styrene block copolymer resin. CONSTITUTION:At least one resin selected from among the following crystalline resins is grafted onto a saturated styrene block copolymer resin to obtain the purpose crystalline styrene block copolymer resin. The above crystalline resins include a polyethylene resin or wax, an oxidized polyethylene resin or wax, a modified polyethylene resin or wax, an ethylene/vinyl acetate copolymer resin of a vinyl acetate content <=19wt.%, an ethylene/ethyl acrylate copolymer resin of an ethyl acrylate content <=15wt.%, an ethylene/acrylic acid copolymer resin of an acrylic acid content <=10wt.%, an ethylene/butylene copolymer, an ethylene/propylene copolymer, natural wax and paraffin wax.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a method for producing a styrenic block copolymer resin that exhibits crystalline properties in a normal state.

Specifically, the present invention relates to a method for producing a styrenic block copolymer that exhibits crystallinity, which has significantly improved compatibility with waxes, is rich in toughness, and can be used as a modifier for resins.

[Prior Art] Up to now, styrene-butadiene-styrene block copolymers, styrene-isoprene-styrene block copolymers synthesized by ionic polymerization methods, and saturated styrene-based polymers having amorphous properties have been synthesized. Block copolymer resins are known, and methods for producing them are well known.

Note that the resin is a non-crystalline linear polymer and is well known as a resin with excellent rubber elasticity.

For example, it is clearly a well-known resin, as evidenced by the fact that manufacturers such as Shell Chemical Co., Asahi Kasei Co., Japan Synthetic Rubber Co., Ltd., and Nippon Zeon Co., Ltd. are engaged in commercial production and sales.

On the other hand, related published technology examples include the production of maleic anhydride grafts by Shell Chemical Co., Asahi Kasei Co., Ltd., etc. as a modification technology for hydrogenated styrenic block copolymer resins exhibiting amorphous properties. I can list the techniques. However, their purposes of use and effects are different.

In 1988, at the TAPPI International Conference in Atlanta, USA, Shell Chemical Co., Ltd. proposed a linear saturated styrene-ethylene-butylene-styrene block in which the intermediate rubber flock had a crystalline ethylene-butylene rubber block. A copolymer is proposed. However, the specific manufacturing method is still completely unknown and has not been disclosed yet.

As described above, there is still no disclosure of a method for producing a styrenic block copolymer that exhibits crystalline properties, and in particular, no inexpensive production method using resins that are easily available on the market as raw materials has yet been found. .

[Problems to be Solved by the Invention] Most of the -tC-type styrenic block copolymer resins obtained by the prior art have polystyrene end blocks, and the middle blocks are amorphous butadiene, isoprene, and ethylene. -butylene or ethylene-propylene rubber chains).

Therefore, when using the conventional styrene-based block copolymer resin as a main component in the field of true melt adhesives, paints, toners, molding resins, etc., the waxes added and blended There was a limit to the compatibility of

In other words, in the case of using it as an adhesive, there was a demand for an adhesive with toughness, and for that purpose, there was a demand for the use of a large amount of amorphous styrenic block copolymer resin obtained using conventional technology.

However, wax compounds such as synthetic waxes such as paraffin wax, microcrystalline wax, and oxidized wax, as well as natural waxes, have limited compatibility, and sufficient adhesive toughness and adhesive durability cannot be achieved. This was a problem.

In addition, in the field of resin compositions for inks for thermal transfer recording, copying, etc., amorphous There was a demand to use more styrenic block copolymer resins.

However, similar to the paper true melt adhesive described above, in cases where the main component is a styrene-based block copolymer resin obtained using conventional technology, there are problems such as compatibility with wax compounds and blocking problems. It happened and it was a problem.

In other words, in markets such as adhesives, toners, paints, and molded resins, we are developing a new saturated polystyrene block resin that is rich in toughness and anti-blocking properties and is highly compatible with wax compounds. It is strongly requested.

Specifically, the purpose is to provide a saturated styrenic block copolymer resin that is compatible with wax compounds and has crystalline properties, and a production method for this purpose that can be easily and inexpensively synthesized. The goal is to provide the following.

More specifically, we provide a side chain saturated styrene block copolymer that develops crystallinity by using a saturated polystyrene block copolymer that is easily available on the market and exhibits amorphous properties. There is something to do.

[Means for Solving the 5 Problems] As a result of intensive research, the present inventor has developed a side-chain saturated styrenic block copolymer having crystalline properties, obtained by the production method shown below. Coalescence significantly improves compatibility with wax compounds such as synthetic waxes and natural waxes.

It has been found that the effect of imparting toughness is high, and that the manufacturing method is simple, easy, and inexpensive6, and the present invention has been achieved.

In other words, the present invention means that a saturated styrenic block copolymer resin contains 19% by weight or less of the following crystalline resin group polyethylene wax, resin oxidized polyethylene wax, resin-modified polyethylene wax, or resin vinyl acetate. Ethylene-vinyl acetate copolymer resin 15f as ethyl acrylate
Ethylene-ethyl acrylate copolymer resin containing 5% or less Ethylene-acrylic acid copolymer resin containing 10% by weight or less as acrylic acid Polyethylene-butylene copolymer Polyethylene-propylene copolymer Natural wax IJm or paraffin wax selected from The resin obtained by the method for producing a crystalline styrenic block copolymer resin obtained by graft polymerization modification using a resin of 2f1 or more satisfies the problems to be solved by the present invention described above. The present invention has been achieved.

More specifically, the present invention provides that a crystalline low-molecular or medium-molecular polyethylene resin is a styrene-butadiene-styrene block copolymer (hereinafter referred to as SBS) and/or
Alternatively, a grafting modification method is applied to a saturated styrenic block copolymer obtained by hydrogenating a styrene-isoprene-styrene block copolymer (hereinafter referred to as SIS), and crystalline segments are attached to the side chains. And as a result,
This is a method for producing a crystalline styrenic block copolymer that has improved compatibility with waxes.

The invention will be described in more detail below.

In view of its intended use, the present invention preferably contains 40% by weight or more of a saturated styrenic block copolymer resin and the following crystalline resin group crystalline resin group polyethylene resin or wax oxidized polyethylene resin or wax modified polyethylene resin or wax. Polyethylene-butylene copolymer Polyethylene-propylene copolymer Natural wax Crystalline styrenic block copolymer obtained by graft polymerization modification of 60% by weight or less of one or more resins selected from paraffin wax.゛Production method of polymer resin is good - In the present invention, more preferably, the saturated styrene block copolymer resin is a styrene-butadiene-styrene block copolymer resin with a polystyrene content in the range of 5 to 60% by weight. A method for producing a crystalline styrenic block copolymer resin using a resin obtained by hydrogenating a polymer and/or a styrene-isoprene-styrene block copolymer is preferred.

Furthermore, in the present invention, the saturated styrenic block copolymer resin has a polystyrene content in the range of 5 to 60% by weight and a weight average content in the range of 2,000 to 200,000.
A method for producing a crystalline styrenic block copolymer resin using a resin formed by hydrogenating a styrene-butadiene-styrene block copolymer and/or a styrene-isoprene-styrene block copolymer is highly preferred.

Further, in the present invention, preferably, the weight average molecular weight is 200 to
100,000 and exhibits crystallinity of at least 30% at room temperature, the following crystalline resin group: Crystalline resin group polyethylene resin or wax oxidized polyethylene resin or wax-modified polyethylene resin or wax A method for producing a crystalline styrenic block copolymer resin using one or more selected from polyethylene-butylene copolymer, polyethylene-propylene copolymer, natural wax, and paraffin wax is preferred.

Furthermore, in the present invention, the weight average molecular weight is in the range of 200 to 100,000, and the crystallinity is at least 3 at room temperature.
1 selected from high-density polyethylene wax, low-density polyethylene wax, oxidized polyethylene wax, modified polyethylene wax, etc. that exhibits crystallinity of 0% or more
Highly preferred is a method of producing a crystalline styrenic block copolymer resin using a crystalline polyethylene wax comprising a species or two or more species.

Further, in the present invention, preferably, a production method using a radical polymerization addition reaction using a radical generator is preferable as the grafting method.

Further, the present invention may preferably be a production method that utilizes a chelate-forming reaction using a chelate-forming agent as the grafting method.

Further, the present invention preferably uses any one of a ring-opening addition reaction, a silyl group condensation reaction, an esterification reaction, an oxidation reaction, a urethanization reaction, an etherification reaction, an amidation reaction, an imidization reaction, etc. as the grafting method. What can be obtained from the manufacturing method used can be adopted without any problems.

Moreover, the present invention may preferably be a manufacturing method in which grafting is performed in a solvent-free system, or a manufacturing method in which grafting is performed in a solvent-based system.

Further, the present invention preferably includes a batch type manufacturing apparatus,
A manufacturing method using a batch-type kneader/Rougu mixer and a manufacturing method using a twin-screw kneading extruder as a continuous manufacturing device are recommended as simple and inexpensive manufacturing methods.

In the present invention, the saturated styrenic block copolymer resin refers to SBS and/or S
A typical example is a resin obtained by hydrogenating IS, which means a resin having polystyrene terminal blocks and an amorphous ethylene-butylene and/or ethylene-propylene rubber block in the intermediate rubber block.

The saturated styrenic block copolymer resin of the present invention is generally easily available on the market, and includes, for example, Shell Chemical Co. (under the trade name Clayton), Asahi Kasei Co. (under the trade name Tuftic), Mitsubishi Yuka Co., Ltd. There are many types of saturated styrenic block polymers available on the market, such as Lavalon (trade name), and there are no problems when using them.

In the present invention, the reason why the above manufacturing method using a saturated styrenic block copolymer resin of 40% by weight or more is preferable is that if the amount is less than 40% by weight, the resulting resin significantly lacks toughness. be.

Furthermore, in the present invention, it is preferable that the polystyrene content of the saturated styrenic block copolymer resin be in the range of 5 to 60% by weight, because if it is less than 5% by weight, the heat resistance rigidity will be poor. This is because if the content exceeds 60% by weight, the toughness will be poor.

Furthermore, in the present invention, as the saturated styrenic block copolymer resin, a resin having a polystyrene content in the range of 5 to 60% by weight and a weight average molecular weight in the range of 2,000 to 200,000 can be used. This is highly preferred because if the weight average molecular weight is less than 2,000, the heat resistance rigidity and toughness will be poor, and if the weight average molecular weight is more than 200,000, the melt viscosity will be extremely high, which is inappropriate.

In the present invention, polyethylene wax or resin as a group of crystalline resins means a relatively low molecular weight polyethylene wax or resin with high density to low density, and is preferably used in the everyiometer method, viscosity method, or chromatography method. The molecular weight determined by etc. is 100,000 or less, more preferably 10,000 or less,
Most preferably, the resin has a crystallinity of 5,000 or less.

In the present invention, polyethylene waxes or resins as a group of crystalline resins include, for example, Mitsui Hywax, a trade name synthesized by the Ziegler polymerization method of Mitsui Petrochemicals, and others synthesized by the 1,1 Ischer-Tropsch method. Synthesized Sasol wax, Allied's A-C bo-phenazine synthesized by high pressure method, etc. can be employed.

In the present invention, oxidized polyethylene wax or resin as a group of crystalline resins refers to oxidized polyethylene wax or resin of high density to low density and relatively low molecular weight, and is preferably measured by the everiometer method or the viscosity method. A crystalline resin having a molecular weight determined by chromatography or the like of IO 0,000 or less, more preferably 10,000 or less, most preferably 5,000 or less is preferable.

In the present invention, the oxidized polyethylene wax or resin as the crystalline resin group includes, for example, Mitsui Hiwax, a trade name synthesized by the Ziegler polymerization method of Mitsui Petrochemicals, and others synthesized by the Finscher-Robutsch method. Resins obtained by oxidizing synthesized Sasol wax, Allied's A-C polyethylene synthesized by high-pressure method, etc. are representative and can be used.

In the present invention, the modified polyethylene wax or resin as a group of crystalline resins means a modified polyethylene wax or resin having a relatively low molecular weight and high density to low density, and is preferably measured by the everiometer method or the viscosity method. A crystalline resin having a molecular weight of 100,000 or less, more preferably 10,000 or less, most preferably 5,000 or less as determined by chromatography or the like is preferred.

In the present invention, modified polyethylene waxes or resins as a group of crystalline resins include, for example, Mitsui Hiwax, a trade name synthesized by the Ziegler polymerization method of Mitsui Petrochemicals, and others synthesized by the Finscher-Robutsch method. low-molecular-weight polyethylene resins such as Sasol wax synthesized using a high-pressure method and Allied's A-C polyethylene,
A typical example is a resin modified with an unsaturated carboxylic acid compound. That is, preferred examples include modified polyethylene in which carboxyl groups, hydroxyl groups, silyl groups, etc. are introduced into the molecule.

In the present invention, the ethylene-vinyl acetate copolymer resin containing 19% by weight or less of vinyl acetate as a crystalline resin group refers to an ethylene-vinyl acetate copolymer resin containing 19% by weight or less of vinyl acetate, which is obtained by a known polymerization technique and has a weight average molecular weight of at most 500,000 or less. , preferably 200,000 or less, more preferably 100,000 or less, a resin in which polyethylene crystalline polymer chains exist in the molecule to the extent that crystallinity can be exhibited.

Further, the vinyl acetate content of the ethylene-vinyl acetate copolymer resin is 19% by weight or less, preferably 10% by weight.
This is because a resin containing 19IIKffi% or more, which is preferably below, can hardly be expected to have crystalline properties, which is a problem.

In the present invention, the ethylene-ethyl acrylate copolymer resin containing 15% by weight or less of ethyl acrylate as a crystalline resin group refers to an ethylene-ethyl acrylate copolymer resin containing 15% by weight or less of ethyl acrylate, which is obtained by a known polymerization technique and has a weight average molecular weight of at most A resin having a boethylene crystalline polymer chain of 500,000 or less, preferably 200,000 or less, more preferably 100,000 or less, which is sufficient to exhibit crystallinity in the molecule, is preferable.

Further, the ethyl acrylate content of the ethylene-ethyl acrylate copolymer resin is preferably 15% or less, preferably 10ffi 1% or less.

This is because a resin containing 15% by weight or more cannot be expected to have crystalline properties, which is a problem.

The above-mentioned ethylene-hinyl acetate co-If polymer resin, ethylene-ethyl acrylate copolymer resin, etc. as the crystalline resin group of the present invention are easily available on the market,
For example, it can be obtained as NUC resin from Nippon Unica, and as Mitsui Evaflex resin from DuPont Mitsui Polychemicals.

The polyethylene-butylene copolymer and polyethylene-propylene copolymer as the crystalline resin group of the present invention are obtained by known polymerization techniques and have a weight average molecular weight of at most 500,000 or less, preferably A resin having a molecular weight of 100,000 or less and having a crystalline polyethylene polymer chain arranged in the molecule so as to exhibit crystalline properties is preferable.

Polyethylene-butylene copolymer, and polyethylene-
Propylene copolymers are mainly produced by random polymerization of ethylene and butylene or propylene to produce a non-crystalline copolymer. It is preferable to use a synthetic method in which polyethylene chains are arranged in a controlled manner.

In the present invention, the natural wax as a group of crystalline resins is a crystalline natural bush, preferably easily available carnauba wax, and the following are representative.

That is, there are animal waxes, vegetable waxes, mineral waxes, and the like. More specifically, typical animal waxes include beeswax, spermaceti wax, and native wax. A typical example of the vegetable wax is carnauba wax. Typical examples of the solid wax include osikelite and montan wax.

In the present invention, paraffin wax as a group of crystalline resins is a crystalline petroleum wax, and representative examples of the petroleum wax include paraffin wax and microcrystalline wax. Preferably, readily available paraffin wax is suitable.

In addition, when natural wax or paraffin wax is used in the production method of the present invention, the above-mentioned crystalline resin group other than natural wax or paraffin wax may be used in combination for the purpose of obtaining a resin with a more favorable balance of physical properties. In the present invention, preferably, among the above-mentioned crystalline resin group, polyethylene wax or resin, oxidized polyethylene wax or resin, modified polyethylene wax or resin,
A method for producing a crystalline polystyrene block copolymer using one or more resins selected from polyethylene-butylene copolymer, polyethylene-propylene copolymer, natural wax, and paraffin wax is preferred; The usage rate is 60! It is preferable to do this within ift%.

The reason why 60% by weight or less is preferable is that if it is more than this, a large amount of unreacted crystalline resin raw material will remain during modification, which is not preferable.

Also, more preferably, among the above-mentioned crystalline resin group,
The weight average molecular weight is in the range of 200 to 200,000, and
The following polyethylene waxes or resins, oxidized polyethylene waxes or resins, modified boreethylene waxes or resins, polyethylene-butylene copolymers, polyethylene-propylene copolymers, which exhibit crystallinity of at least 30% or more at room temperature. The reason why the method for producing a crystalline polystyrene block copolymer using one or more resins selected from natural waxes, paraffin waxes, etc. is good is that the properties of the resulting resin are This is because viscosity suitability, balance between heat resistance and toughness, etc. are preferable.

Also, most preferably, among the above-mentioned crystalline resin group,
One or more resins selected from polyethylene wax or resin, oxidized polyethylene wax or resin, modified polyethylene wax or resin, and preferably have a weight average molecular weight in the range of 200 to 200,000. The amount of usage L indicated in the problems to be solved by the present invention was
1 (in the field of adhesives for paper, resin compositions for ink, etc.), it is optimal as a resin that fully satisfies the requirements.

The modification method that can be adopted in the production method of the present invention may be carried out by employing known techniques, and although it is not particularly limited, the following modification methods may be adopted, and an easy, simple, and inexpensive method may be selected. It's good to do that.

That is, a preferred example of the grafting method is a graft polymerization modification method using a radical generator. Modification using a so-called radical polymerization addition reaction in which thermal decomposition radicals of an organic peroxide catalyst are generated in a nitrogen stream, and as a result, the above-mentioned crystalline resin group is grafted onto a saturated styrenic block copolymer. Synthetic methods are preferred.

Examples of the radical generator include organic peroxides, ozone, hydrogen abstracting inorganic compounds, electron beams, and light.

The organic peroxide catalyst may be a known olefin monomer polymerization initiator, preferably 20
The following catalysts exhibiting activity at temperatures below 0°C are representative.

That is, it may be carried out by selecting one from ketone peroxide, peroxy ester, dialkyl peroxide, hydroperoxide, diacyl peroxide, peroxyketal, peroxydicarbonate, and the like. More preferably, by selecting an active radical species having a half-life of 0.01 to 10 hours in the range of 120°C to 180°C, +M fat can be melted completely uniformly (uniformly) in a solvent-free system. B) This is a good example because it can be carried out.

Further, as the hydrogen abstracting inorganic compound catalyst, Se
(Tetravalent) compounds are most representative.

In addition, as an alternative grafting method, a production method utilizing a chelate formation reaction using a known chelate forming agent may also be adopted. Organometallic compounds from groups 4 to 8 are common.

Furthermore, as another grafting method, a known method,
Namely, ring-opening addition reaction, silyl group condensation reaction, esterification 1 reaction, oxidation reaction, urethanization reaction, etherification reaction,
It may be obtained by a manufacturing method that utilizes either amidation reaction or imidization reaction, and as a result, by either grafting method, a side chain structure is formed on an amorphous saturated styrenic block copolymer. Any method may be used as long as a crystalline styrenic block copolymer is obtained by graft polymerization addition of a crystalline polymer such as crystalline polyethylene wax as described above.

When carrying out the polymerization addition reaction of the present invention, there are no restrictions on the system and production equipment, and any system or production equipment that allows the desired grafting reaction to proceed smoothly may be used.

That is, it may be a non-solvent type or a dilute solvent type using a solvent, and may be appropriately selected depending on the type of manufacturing equipment.

Preferably, a solvent-free system can be used in manufacturing using a heating Banbury type mixer or a Banbury type kneader/ruder as a batch type manufacturing device, and preferably has strong turbine blades. In the case of reaction vessels, etc., it is often required that the viscosity of the system be lowered or homogenized quickly, so it is preferable to use a solvent, and after adjustment, a defoaming agent is applied. 1
00% resin.

Moreover, it is natural that a synthesis method using a continuous production device is more preferable, and for that purpose, a synthesis method using a twin-screw kneading extruder called a continuous kneader is preferable. It is also preferable to supply the raw material resin by finely pulverizing it in advance and blending it uniformly, or to use a 0-division multistage reaction method in which any component is pumped to the middle part of a kneading extruder and the reaction is carried out. It is given as an example of synthesis. Of course, there is no equivalent problem in carrying out the continuous method without a solvent or in a solvent system.

When using a solvent system, for the raw material resin of the present invention,
As long as the solvent can be heated, there will be no problem. It is preferable to use a low boiling point solvent with a boiling point of less than 200°C. If the solvent has a boiling point of 200°C or higher, the solvent will not be present in the resulting resin. This is because it tends to remain and cause problems.

Examples of such solvents include acetone, methyl ethyl ketone, isobutyl ketone, cyclohexanone, isophorone, ketones such as acetophenone, cyclohexanol, alcohols such as isopropyl alcohol, ethyl acetate, acetoacetic esters, and ethylene glycol motubutyl ether. Furans such as tetrahydrofuran, halogen compounds such as methylchloroform, trichloroethane, and tetrachloroethylene, aromatic hydrocarbons such as benzene, toluene, xylene, styrene, and mineral spirits, and fats such as n-hexane, n-octane, and cyclohexane. Hydrocarbons, etc. are representative, and one or two of these may be selected and used.Generally, when selecting a solvent type, the compatibility with the raw material resin is the basis. Therefore, it is customary to select and use a solvent that does not impede the grafting reaction, but conversely, it is customary to select and use a solvent that does not impede the grafting reaction, but conversely, it may be added and used as a reaction regulating substance or reaction termination substance for the purpose of stopping or controlling the reaction. Furthermore, the purpose of using the solvent may be to simply use it as a means for supplying resin or as a means for discharging resin, so that a stable and reproducible synthesis method can be achieved. , it is preferable to select and adopt them as appropriate.

Furthermore, as a condition for grafting in the present invention, the reaction temperature is not particularly limited, but it is preferably lower than the temperature at which the raw material resin starts to significantly thermally decompose, and is generally 250°C.
or less, preferably 200°C or less, more preferably 15
A temperature below 0°C is best.

Furthermore, as conditions for the grafting of the present invention, the reaction pressure is not particularly limited; for example, the reaction may be carried out under pressure under nitrogen or conversely under vacuum.

Furthermore, during the synthesis of the present invention, known additives such as antioxidants, ultraviolet stabilizers (absorbing agents), coupling agents, and reaction terminators (inhibitors) may be appropriately added and blended.
Particularly at the end of the synthesis, it is highly preferred to add said additives to the system to stabilize the resin.

Crystallinity in the present invention refers to
Amorphous refers to a phenomenon in which a thermal melt absorption peak is observed in the range of 'C', while amorphous refers to a phenomenon in which a thermal melt absorption peak is hardly observed in a differential scanning calorimeter.

Further, the crystalline styrenic block copolymer resin of the present invention may be thermoplastic or finally thermosetting resin.

The effects of the present invention are that a new tough crystalline styrenic block group polymer that is highly compatible with wax compounds such as synthetic waxes and natural waxes can be easily and inexpensively produced. It has the characteristic of being able to be synthesized.

Since the object of the present invention can be achieved using raw materials that are relatively easily available on the market, it has great advantages on the market.

In other words, non-crystalline saturated styrenic block copolymers have been used in the field of paper hot-melt adhesives that use large amounts of wax components, ink resins, and polymer composite modifying resins. By being able to exhibit functions and effects that could not be obtained through combination, that is, the above-mentioned excellent functions and effects, new developments in industry can be expected.

〔Example〕

EXAMPLES Hereinafter, in order to explain the present invention more specifically, Examples and Comparative Examples will be given and explained, but the present invention is not limited to these Examples.

Further, in the examples below, % and parts mean % by weight and parts by weight, respectively.

Also, the test methods described in the examples of the present invention will be described first.

Stretching followability test> 100 parts of a mixture of the resin obtained in the example of the present invention or a comparative resin and a wax compound at a mixing ratio of 1=3 was completely melted and mixed, defoamed, and made into a mixture of 10 mm in width, 2 mm in thickness, The mixture was poured into a shaping tray with a length of 100 mm, and cooled and solidified to obtain a test piece.

The obtained test piece was pulled at room temperature using a universal tensile testing machine at a pulling speed of 2 mm/min, the tensile distance until breakage was measured, and the elongation rate (%) was calculated.

<Melt viscosity measurement> Measurement was carried out using a Brookfield digital viscometer with rotor No. 21.

(Softening point measurement) Expressed as a measured value using the ring and ball method.

Example 1 A commercially available amorphous saturated styrenic block copolymer resin with 13% polystyrene end blocks (Shigoru Chemical Co., Ltd. Product/trade name Clayton G-16
57) 6,500 parts and commercially available high-density polyethylene wax (product of Mitsui Petrochemicals, average molecular weight 19 determined by viscosity method)
EXAMPLE 1 3,500 parts of 00 (trade name: 1 well Hiwax 200P; a waxy resin with a crystallinity of 90% as determined by X-ray diffraction method) were melt-kneaded at 135°C to 140°C in a nitrogen stream.

To this system, 30 parts of dicumyl peroxide was divided into 3 parts and 1
Graft polymerization addition reaction is carried out by adding at intervals of 0.
After the reaction, the system temperature was further raised to 180°C to completely deactivate the peroxide catalyst, and then pentaerythrityl-tetrakis [3-(3,5-di-butyl-4) was added as an antioxidant. -Hydroxyphenyl)propionate]
The resin obtained by adding and mixing 30 parts of
As measured by HPLC (hereinafter abbreviated as HPLC), most of the copolymer was a saturated styrenic block copolymer (X-1) having graft-modified crystallinity.

As a result of analysis using a differential analyzer, it was found that the X-1 resin obtained by preparative purification by HPLC had a heat of dissolution absorption peak at a position almost similar to the measurement results for crystalline polyethylene alone.

In addition, the crystallinity according to the chi-ray diffraction method is approximately 25 to 2.
It was 8%.

The X-1 resin was subjected to the tensile followability test shown in Table 1, and the results are shown in (A) of Table 1.

Table 2 (A) shows the softening point and melt viscosity measurement results of the composition with the wax compound.

Example 2 The high-density polyethylene (trade name: Pywax 200P) used in Example 1 was replaced with low-density polyethylene (Mikata Petrochemical Products, molecules determined by the viscosity method [2000, trade name: Mikata Hiwax 220P]). :Crystallinity 7 by X-ray diffraction method
In the same manner as in Example 1 except that 0%) was used,
A saturated styrenic block copolymer (X-2) having crystalline properties was obtained.

Further, as a result of the same treatment and measurement as in Example 1, the degree of crystallinity due to the X-2 resin was over 15%. In addition, χ-2 resin is
It was subjected to the tensile followability test described in Table-1, and the results are shown in (B,) of Table-1.

Further, Table 2(B) shows the softening point and melt viscosity measurement results of the composition of the X-2 resin and the wax compound.

Example 3 (Comparative Example) A composition using a commercially available amorphous saturated styrenic block copolymer resin, that is, (C) listed in Table 1, was prepared using Shell Chemical Products, trade name Kraton G-1657. , In (D) of Table 1, Asahi Kasei product/trade name Toughtic M-1
913 to create a mixture with a wax compound,
It was subjected to a tensile followability test. The results are shown in Table 1 (C).
, described in (D).

Example 4 (Comparative Example) As general-purpose resins other than commercially available amorphous saturated styrenic block copolymer resins, (E) in Table 1 lists typical ethylene-vinyl acetate copolymer resins. , product of Mikata DuPont Polychemical Co., Ltd., trade name Evaflex #4
10, and in (F) of Table 1, a mixture with a wax compound was prepared using Shiraki Unica's product, trade name NUC-6170, as a representative ethylene-ethyl acrylate copolymer resin. It was subjected to a tensile followability test.

The results are shown in (E) and (F) of Table 1.

From the results in Tables 1 and 2, it can be seen that the saturated styrenic block copolymer resin with full crystallinity obtained in the example of the present invention has extremely good compatibility with wax compounds even when solidified, and has a large amount of wax. Even systems containing compounds showed excellent elongation followability and bending properties.

(These physical properties were completely unobtainable with conventionally known non-crystalline saturated styrenic block copolymer resins.) Also, from the results of melt viscosity characteristics and softening point temperature characteristics in Table 2, excellent It has properties that can be used as a resin composition for thermal transfer or as a true melt adhesive composition for paper. I recognized it.

On the other hand, in the case of the amorphous saturated styrenic block copolymer resins shown in (C) and (D) in Table 1 (known resins obtained by conventional techniques), the phase with the wax compound occurs during solidification. The solubility was extremely poor, microscopic phase separation was observed, there was no toughness effect, and only a hard and brittle composition was obtained.

Comparative examples using ethylene-vinyl acetate resin and ethylene-ethyl acrylate resin show that the compatibility with wax compounds is fair, but low concentration resin compositions (used for the purpose of imparting toughness) The elongation followability was extremely low, and only hard and brittle properties were obtained, which was a problem.

In this case, it has been confirmed that when the resin concentration is high (60% or more), the elongation followability is somewhat improved throughout the thickness, but the viscosity becomes high and the stickiness is strong at room temperature, so it is difficult to use in the coating and ink fields. Blocking properties tend to be poor, which is a problem.

Example 5 A 2-inch twin-screw kneading extruder that can be heated (the kneading paddles were set to have an average residence time of 10 minutes,
A non-crystalline saturated styrenic material with 28% polystyrene end blocks and 2% maleic anhydride addition rate, which was caulked and finely ground using a continuous kneader manufactured by Kuriki Iron Works Co., Ltd. Block copolymer resin (Shell Chemical Products, trade name Kraton FG-1901X) 7000
and low-density acid-modified polyethylene wax (product of Mikata Petrochemical Co., Ltd., average molecular weight 1500 determined by viscosity method, trade name Mikata Hiwax 11'05A: Wax-like product with crystallinity of 60% determined by X-ray diffraction method) 3,000 parts of resin), 15 parts of benzoyl peroxide, and 5 parts of zinc salt of acetylacetone were uniformly blended in a Henschel mixer and continuously fed from a hopper, and heated to 110°C to 120°C.
The resin obtained by continuous production by simultaneously performing melt kneading and graft addition reaction (radical addition reaction and chelate formation reaction) at a tank temperature of
Most of it was a saturated styrenic block copolymer (X-3) having grafted and modified crystallinity.

As a result of analysis with a differential scanning calorimeter, preparative t# by HPLC
In the produced X-3 resin, a heat of dissolution absorption peak was observed at a position almost similar to the measurement results for crystalline low-density polyethylene alone.

In addition, the crystallinity according to X-ray diffraction method is approximately 15 to 1.
It was 6%.

The X-3 resin was subjected to the tensile followability test described in Table 3, and the results are shown in (G) of Table 3.

Example 6 The high-density polyethylene wax (trade name Hiwax 200P) used in Example 1 was replaced with low-density polyethylene wax (Mikata Petrochemical Products).

A product having a molecular weight of 1000 determined by a viscosity method and having a trade name of Mikata Hiwax 110P (which shows a degree of crystallinity of 80% by an X-ray diffraction method) was used.

On the other hand, amorphous saturated styrene - ethylene - butylene -
Styrene block copolymer resin (trade name Kraton C;-
1657), an amorphous saturated styrene-ethylene-propylene block copolymer resin with a 37% styrene content (Shell Chemicals, Kraton G-1701X)
A saturated styrenic block copolymer (X-4) having crystalline properties was obtained in the same manner as in Example 1 except for the following.

Further, as a result of the same treatment and measurement as in Example 1, the degree of crystallinity due to X-4#A fat was over 20%.

In addition, the X-4 resin was subjected to the tensile followability test described in Table 3, and the results are shown in (H) of Table 3.

Example 7 Amorphous saturated styrene-ethylene-butylene-styrene block copolymer resin having 20% polystyrene end blocks into which 2% active silyl groups have been introduced (styrene chemical product, trade name Tuftic H-1052) ) and 150 parts of a pre-modified reactive resin of 150 parts of a pre-modified high density polyethylene wax (
Mikata Petrochemical Co., Ltd. product/average molecular weight determined by viscosity method: 400
0 (trade name: Mikata Hiwax 400P): 100 parts of a reactive polyethylene wax with active hydroxyl groups, which is obtained by oxidizing Mikata Hiwax 400P (crystallinity: 85% as determined by X-ray diffraction method), is mixed in a 1:1 ratio of toluene and mineral spirit. A 30% dilute solution of the solvent was prepared in a 2 liter 470 flask in a nitrogen stream at a heating temperature of 135°C to 140°C.
Grafting reaction was carried out by carrying out demethanol reaction for a period of time.

After the reaction, the system temperature was further raised to 180'C to remove the solvent, and after the reaction and solvent removal were complete, pentaerythrityltetrakis [3-
(3,5-di-t-butyl-4-hydroxyphenyl)
The resin obtained by adding and mixing 2 parts of propionate] is HP
As measured by LC, most of the saturated styrenic block copolymer (X-
5).

As a result of analysis at a differential calorific value of 81, it was found that the X-5 resin obtained by preparative purification by HI'LC had a heat of dissolution absorption peak at a position almost similar to the measurement results for crystalline polyethylene alone.

In addition, the crystallinity according to X-ray diffraction method is approximately 25~
It was 28%.

The X-5 resin was subjected to the tensile followability test shown in Table 1, and the results are shown in Table 3 (+).

In Example Date Table 3 (J), a resin composition with a wax compound using Shell Chemical Products Kraton G-1701X as a non-crystalline saturated styrene-ethylene-propylene block copolymer resin was used as a comparison resin. (The resin is indicated as G-1701).

〔Effect of the invention〕

From the results in Tables 1 and 2, it is clear that the saturated styrenic block copolymer resin that exhibits crystallinity obtained in the examples of the present invention has extremely good compatibility with wax compounds even when solidified, and contains a large amount of wax compounds. Even the system containing this compound showed excellent elongation followability and bending properties.

Furthermore, from the results of the melt viscosity properties and softening point temperature properties shown in Table 2, it was confirmed that the properties were sufficient to allow use as an excellent resin composition for thermal transfer or as a hot melt adhesive composition for paper.

On the other hand, in the case of the amorphous saturated styrenic block copolymer resins shown in (C) and (D) in Table 1 (known resins obtained by conventional techniques), the phase with the wax compound occurs during solidification. The solubility was extremely poor, microscopic phase separation was observed, there was no toughness effect, and only a hard and brittle composition was obtained.

In addition, when looking at comparative examples using ethylene-vinyl acetate resin and ethylene-ethyl acrylate resin, the compatibility with the wax compound is fair, but low concentration resin (used for the purpose of imparting toughness) & Il composition However, the elongation followability is extremely low, and only hard and brittle properties can be obtained.
That was a problem.

In this case, it has been confirmed that a high concentration of resin (60% or more) exhibits some elongation followability, but it becomes highly viscous and sticky at room temperature, making it difficult to block in the coating and ink fields. This was a problem because it was easy to have poor performance.

From the results in Table 3, it is clear that the crystalline saturated styrenic block copolymer resin obtained by the method of the present invention has the effect of imparting toughness, which has not been achieved with saturated styrenic block copolymer resins to date. Obtained.

Also, as shown in the examples of the present invention, what is the manufacturing method in particular? j! It was confirmed that the obtained new crystalline saturated styrenic block copolymer resin, which is clearly not complicated and can be produced at low cost, is a useful resin in various market fields.

Table-1 Table-2 O:RwAIlO'following'f'J>' 5-30%
Explanation of key codes for Japanese lilies (Table-1,
3 common) Paraffin wax: Japan; Ja Kazu 3 TomikHNP-3 Chu H Hiwatukusu: Roy 4 #廓d3 Yīcho NFS-9
210 Microcrystalline Wax: Japanese Sukihato Old M? h
Hl -M i c l O80 Carnauba Wax
：Natural wax from Brazil Polyethylene wax：Product name of Sasol CI wax Polypropylene wax of Sasol Corporation, processed by Fischer Troputsch method：=i-uM＞Viscol 55
0P (However, x-1, χ-24 according to the present invention and waxing ratio -18:82) Code explanation Wax-1: 30% of Japanese O#n End Old 1kikHNP 3 as paraffin wax and 20% Nippon i/7W long NFS-9210 as oxidized wax, and Hiki Joden Miku, Hl-Mi as microcrystalline wax.
Wax consisting of 50% c1080.

Fufusu 2: 30% of Brazilian natural wax as carnauba wax and Nippon Seidan old 1 as oxidized wax.
Prefecture kN P S 9210 at 20% and Japanese tn pigeon former 1ro kHi-M as microcrystalline wax.
A wax consisting of 50% ic 1080.

Claims (1)

[Claims] 1. A crystalline product obtained by graft polymerizing and adding one or more resins selected from the following crystalline resin group to a saturated styrenic block copolymer resin. A method for producing a styrenic block copolymer resin. Crystalline resin group Polyethylene resin or wax oxidized polyethylene resin or wax modified polyethylene resin or wax Ethylene-vinyl acetate copolymer resin containing 19% by weight or less as vinyl acetate Ethylene-ethyl acrylate copolymer resin containing 15% by weight or less as ethyl acrylate Ethylene-acrylic acid copolymer resin containing 10% by weight or less as acrylic acid Polyethylene-butylene copolymer Polyethylene-propylene copolymer Natural wax Paraffin wax 2, saturated styrenic block copolymer resin containing 40% by weight or more, and the following: Production of the crystalline styrenic block copolymer resin according to claim 1, characterized in that 60% by weight or less of one or more resins selected from the group of crystalline resins is obtained by graft polymerization modification. Method. Crystalline resin group polyethylene resin or wax oxidized polyethylene resin or wax modified polyethylene resin or wax polyethylene-butylene copolymer polyethylene-propylene copolymer natural wax paraffin wax 2, as saturated styrenic block copolymer resin, polystyrene content is A claim characterized in that a resin formed by hydrogenating a styrene-butadiene-styrene block copolymer and/or a styrene-isoprene-styrene block copolymer in a range of 5 to 60% by weight is used. Item 3. A method for producing a crystalline styrenic block copolymer resin according to item 1 or 2. 4. As a saturated styrenic block copolymer resin, a styrene-butadiene-styrene block copolymer having a polystyrene content in the range of 5 to 60% by weight and a weight average content in the range of 2,000 to 200,000; and/or a resin obtained by hydrogenating a styrene-isoprene-styrene block copolymer.
The method for producing the crystalline styrenic block copolymer resin described above. 5. The weight average molecular weight is in the range of 200 to 100,000,
Claims 1 to 4, characterized in that the crystallinity is made of one or more selected from the following crystalline resin group, which exhibits crystallinity of at least 30% or more at room temperature. A method for producing a crystalline styrenic block copolymer resin according to any of the above. Crystalline resin group polyethylene resin or wax oxidized polyethylene resin or wax modified polyethylene resin or wax polyethylene-butylene copolymer polyethylene-propylene copolymer natural wax paraffin wax 6, weight average molecular weight is in the range of 200 to 100,000 , using one or more types selected from high-density polyethylene wax, low-density polyethylene wax, oxidized polyethylene wax, modified polyethylene wax, etc., which exhibit a crystallinity of at least 30% or more at room temperature. 3. The method for producing a crystalline styrenic block copolymer resin according to claim 1 or 2, characterized in that a crystalline polyethylene wax consisting of: 7. A method for producing a crystalline styrenic block copolymer resin according to any one of claims 1 to 6, wherein a radical polymerization addition reaction using a radical generator is used as the grafting method. 8. A method for producing a crystalline styrenic block copolymer resin according to any one of claims 1 to 7, wherein a chelate-forming reaction using a chelate-forming agent is used as the grafting method. 9. Grafting methods include ring-opening addition reaction, silyl group condensation reaction, esterification reaction, oxidation reaction, urethanization reaction,
A method for producing a crystalline styrenic block copolymer resin according to any one of claims 1 to 8, which utilizes any one of etherification reaction, amidation reaction, imidization reaction, etc. 10. Claims 1 to 9, wherein the grafting is carried out in a solvent-free system.
A method for producing a crystalline styrenic block copolymer resin within any of the ranges described above. 11. Claims 1 to 10, wherein the grafting is carried out in a solvent system.
A method for producing a crystalline styrenic block copolymer resin within any of the ranges described above. 12. A method for producing a crystalline styrenic block copolymer resin according to any one of claims 1 to 11, using a kneader-ruder kneader as the batch-type production device. 13. A method for producing a crystalline styrenic block copolymer resin according to any one of claims 1 to 12, using a twin-screw kneading extruder as the continuous production device.