JPS5884808A - Preparation of resinous material - Google Patents

Abstract

PURPOSE:To prepare a resinous material without causing the phase separation even on melting under heating, by copolymerizing a monomeric component consisting of an unsaturated polyfunctional carboxylic acid anhydride and another monomer in a melt of a compound having a hydroxyl group and a specific melting point. CONSTITUTION:(A) A monomeric component consisting of (i) an unsaturated carboxylic acid anhydride, e.g. maleic anhydride, and (ii) another monomer, e.g. a vinyl ester, is copolymerized in (A) a melt of a compound, e.g. a partial fatty acid ester of a polyhydric alcohol, having hydroxyl groups and <=150 deg.C melting point preferably at 1:(0.001-0.5) weight ratio between the components (A) and (i) and 1:(0.1-10) weight ratio between the components (A) and (B), and if necessary an additive, e.g. a filler, tackifier or colorant, is mixed therewith to prepare the aimed resinous material. USE:Adhesives, binders, etc.

Description

[Detailed description of the invention] Zero shot f! 4Fi, a method K for producing a resinous material that does not cause phase separation even when heated and melted.

Compositions made by blending wax-like substances with thermoplastic polymers can be used as adhesives, binders, and other applications Kj6
However, the problem with practical soils is that the heated molten material undergoes phase separation over time.

Although it is possible to mechanically stir Fi to prevent phase separation, this is inconvenient in use, and mechanical stirring is often not possible depending on the mode of use.

The present invention solves these conventional problems and aims to provide an Al-like material that does not undergo phase separation even in a molten state for a long time.

The present invention relates to a compound having a hydroxyl group and a melting point of 150°C or less (
4) In the Sm solution, unsaturated polycarboxylic anhydride (bl
) and other nanatsumers (monomer components consisting of b riyosho) are copolymerized.

In the polymerization reaction of (b) in the melt of this polymer, (b)
l) When a copolymer is obtained from the ri component and the (b8) component, co-K is produced, and the esterification reaction between the (bt) component and the hydroxyl group of (4) in the round thread polymer occurs, and the ( It is presumed that the transesterification reaction between the ester groups of bl)vi and min and the ester group also occurs in parallel, and the resulting reaction product has a complex chemical composition.

The witMI-like substance obtained by the method of the present invention can have various properties depending on the type of substance (injuga) or the ratio of (AI and 俤), but typically it has a waxy appearance with a white and opaque appearance. This glossy material melts at a certain temperature when heated and exhibits sharp melting behavior. This substance exhibits the remarkable effect of not causing phase separation even in the molten state [I] for a long time.

As the compound (3) containing a swimsuit group and having a melting point of +50°C or higher, compounds that are solid or liquid at room temperature, and among others, those that have waxy properties and a melting point of 50 to 150°C, such as polyvalent Partial molecules of al-7-yl fatty acids can give.

Among these, I+h fatty acid esters with an OH value of 20 or more,
Particularly important are saturated polyesters with an OH value of 20 or more.

If the melting point exceeds 150℃, (B
The polymerization of 1 is difficult in practice and is unsuitable for the purpose of clarity. Moreover, those having no hydroxyl group are unsuitable for the purpose of the present invention since the resinous material obtained by copolymerization causes phase separation when melted.

As the unsaturated polycarboxylic anhydride (BL) constituting the monomer component (8), maleic anhydride, itaconic anhydride, citraconic anhydride, glutafic anhydride, etc. are used.

Other monomers (b J include vinyl ester, unsaturated monocarboxylic acid or its ester, salt, amide, nitrile, unsaturated dicarboxylic acid or its monoester, diester, salt, unsaturated sulfonic acid or its salt, styrene Examples of these include thread pickers, vinyl ethers, vinyl chloride, etc. Among these, vinyl esters, styrene, acrylic esters, and meccrylic esters are particularly important. It is also possible to use a small amount of various polyfunctional heptamers including .

In 11JI, the copolymerization of (b, ) and (b□) is carried out in the melt of (b, ) and (b□). It also functions as a filter medium and as a reactant.

Copolymerization is usually carried out using a radical polymerization initiator.

The ratio of usage of prison and @) can vary widely, but (4) and (bl
) with weight ratio of 1: 0.001 to 0.5, preferably #-i1: 0.005 to 0.5,
If the ratio of (bl) is too small, the resulting resinous material will be likely to undergo phase separation during heating and melting, while if the ratio of (bJ) is too large, it will be difficult to control the copolymerization reaction of (b, ) and (b2). . Moreover, the weight ratio of (4) and ) is I:0.
It is preferable to set the ratio to 1 to 10. If the ratio of [Yes]) is too small, uniformity can be maintained, but the character of the head becomes dominant and practicality becomes difficult. The viscosity of the system during and after polymerization becomes too high; the reactants typically have a white or slightly colored opaque waxy appearance at room temperature.

In the present invention, during the copolymerization reaction or after the #-1 reaction, various additives such as fillers, tackifiers, colorants, reinforcing fibers, plasticizers, surfactants, etc. can be appropriately added. It can also be mixed with other resins.

The resinous material obtained by the method of the present invention can be used as hot melt adhesives, pressure-sensitive adhesives, paper processing agents, fiber processing agents, paint vehicles, ink vehicles, toner binders, ceramic binders, etc. It can be used for.

Next, the method of the present invention will be further explained with reference to Examples.

Example 1 500 parts of glycerin heptanostearate (4) with a valence of 180 [Misaki KOH] and a melting point of 78°C was charged into a flask and heated to 95°C to melt it, and while stirring, maleic anhydride (bl) 15 part, methyl methacrylate)
250 parts and 2-ethylhexyl acrylate) (b'
t) 6 parts of 2s were added, and further 7 parts of benzoyl peroxide were added, and polymerization was carried out at 95 to 100°C for 8 hours. After the reaction was completed, the reaction product was taken out from the flask and allowed to cool, yielding a white opaque waxy block.

This block was packed into a test tube, heated to 160°C, remelted, and left at the same temperature for 24 hours, but the molten liquid remained a homogeneous layer without phase separation and was round.

Comparative Example 1 (b, ), (bri) and (bz) in Example 1 were polymerized in toluene using benzoyl peroxide, and a copolymer was obtained by removing toluene.

500 parts of this copolymer and 500 parts of (A) from Example 1 were heated to 150°C, mixed and melted, and stirred well. When the stirring was stopped and the mixture was left at the same temperature, the phase separated into two layers in about 15 minutes. woke up.

Control Example 2 Copolymerization of (b2) and (b″2) in the presence of a prisoner was carried out in the same manner as in Fi Example 1 except that (bl) was not used.
The resulting block phase separated into two layers in about 15 minutes upon melting.

Example 2 600 parts of a saturated polyester (3) with an oH value of A5 [5vKOH] and a softening point of 60°C was charged into a flask and heated to 90°C to melt it, and while stirring, 25 parts of maleic anhydride (BL) and methyl methacrylate were added. (b,) 250 parts and 550 parts of propionic vinyl (b6) were added, and further 5 parts of benzoyl peroxide were added, and polymerization was carried out at 90 to 110°C for 8 hours. After the reaction was completed, the reaction product was taken out from the flask and allowed to cool, yielding a white opaque block.

This block was packed into a test tube, heated to 130°C, remelted, and left at the same muddy temperature for 24 hours, but the molten # maintained a uniform layer and no phase separation occurred.11 Control Example 6 A copolymer was obtained by polymerizing (bri, (b=), and (b) in Example 2 using benzoyl peroxide in toluene, and removing toluene.

600 parts of this copolymer and 1600 parts of (A) of Example 2 were mixed and melted by heating to 150°C, and after stirring well, the stirring was stopped,
When left at the same temperature, phase separation occurred into the 2' layer at about 15 IIj.

Control Example 4 Copolymerization of (-) and (Q) in the presence of a prisoner was carried out in the same manner as in Example 1 except that (b,) was not used. The layers separated.

Example 3 Glycerin tri-12- and droxystearate (hydrogenated hydrogenated castor oil) with oH value 160 [■KO1(), melting point 84°C] (1500 parts of A were charged in 7 Cusco and heated to 95°C)
Melt itaconic anhydride (b,) under stirring by heating to
20 parts, 550 parts of styrene (bz) and 50 parts of 1]-butyl acrylate (t4+) were added, and further 15 parts of benzoyl peroxide was added, and polymerization was carried out at 90 to 110°C for 8 hours. Reactant after reaction route r When the mixture was removed from the flask and allowed to cool, a white opaque waxy block was obtained.

This block was packed into a test tube, heated to 1'50°C, remelted, and left at the same temperature for 24 hours, but the molten liquid remained a uniform layer and no phase separation occurred.

Claims (1)

[Scope of Claims] 1. In a melt of a compound having a hydroxyl group and a melting point of 150°C or less, a monomer component consisting of unsaturated polycarpodic acid anhydride (bl) and other heptamers (b) ) and (bl) have a weight ratio of 1:0.001 to
0.5. 182. The method according to claim 181, wherein the weight ratio of &(A) and (2) is 1:0.1-10. 4. The method according to claim IIInt, wherein (A) is a compound exhibiting waxy properties. 5. The method according to claim 4, wherein the compound exhibiting wax properties is a fatty acid ester having an OH value of 20 or more. 6. Method 1 according to claim 4, wherein the compound exhibiting wax properties is a saturated polyester having an OH value of 20 or more.
．． 7. The method according to claim 1, wherein (bt) is maleic anhydride. 2. The method according to claim 1, wherein a and (bt) are anhydrous italic acid.