JPS62240334A - Plasticizer - Google Patents

Abstract

PURPOSE:To provide a plasticizer composed of an ester compound of a 2- acyloxy-benzoic acid having a specific structural formula or its derivative and capable of giving a heat-sensitive sticking composition, etc., having improved blocking property, sticking property and adhesivity. CONSTITUTION:A plastizer composed of the compound of formula I [R1 is (halogenated) alkyl, cycloalkyl, alkenyl, (substituted) aralkyl or (substituted) aryl; R2 is alkyl, cycloalkyl, (substituted) aralkyl or (substituted) aryl; R3 is alkyl, aryl or halogen; n is 0-4] (e.g. the compound of formula II). The compound of formula I can be produced e.g. by reacting salicylic acid or its derivative with an alcohol in the presence of a catalyst to esterify the carboxyl group and reacting the product with an active derivative of a carboxylic acid thereby acylating the hydroxyl group.

Description

DETAILED DESCRIPTION OF THE INVENTION Field of the Invention This invention relates primarily to novel plasticizers useful for plasticizing polymers.

In particular, the features of the present invention are best exhibited in compounds that are solid at room temperature but become liquid upon heating and exert a plasticizing action on the polymer. That is, when the polymer is plasticized by the plasticizer of the present invention, it becomes soft at room temperature if the plasticizer is liquid at room temperature, or under heating if it is solid, and becomes sticky (tackiness) when it is plasticized. ) and can be used as an adhesive or adhesive.

Particularly, when the polymer coexists with the plasticizer of the present invention, and more preferably with an adhesion agent, it is useful as a pressure-sensitive adhesive composition if the plasticizer is liquid, or as a heat-sensitive adhesive composition if it is solid. Therefore, in the latter case, the adhesiveness remains for a long time even after leaving the heat source, and it can be used as an adhesive/adhesive for various objects to be blued for a long time. Therefore, (a) polymer before heating , 1 sip) A composition comprising fine particles of a solid plasticizer of the present invention, more preferably an adhesion promoter, is provided in a layered manner on a sheet-like substrate such as paper or film. If so, it will be useful as a heat-sensitive adhesive sheet.

Of course, if a liquid plasticizer among the plasticizers of the present invention is used, it will be useful as a pressure-sensitive adhesive sheet.

The new plasticizer of the present invention is of course useful for general plasticizer applications, and can be used for the purposes of melting, swelling, softening, and thermoforming plastics, and is useful for non-polymer organic compounds. For example, it is useful as a solvent for various foggers in silver halide color photographic materials based on the Fisher method, or as a solvent for colorless dyes and organic solid acids in carbonless pressure-sensitive recording paper. .

In addition, if you select and use a solid material that is solid at room temperature, 10
It can also be used as a sensitizer for color-forming heat-sensitive recording materials (ico-dye/organic solid acid).

(H) Conventional technology Heat-sensitive adhesive compositions are non-adhesive at room temperature, but become tacky when activated by heating, and often persist for a period of time even after being separated from the heat source, resulting in various types of adhesive properties. It is capable of adhering to or adhering to objects.

That is, by applying the above-mentioned composition onto a substrate (base sheet) such as paper or film, a heat-sensitive adhesive sheet such as a heat-sensitive label or a heat-sensitive seal can be obtained. Since the pressure-sensitive adhesive sheet of 2008 is adhesive at room temperature, a protective sheet called @katagami is indispensable, whereas the heat-sensitive adhesive sheet does not require such a protective sheet and is therefore economical and saves SL. It has been attracting attention in recent years as an advantageous user seat.

Typical examples of the 11M class and t ratio of chemical materials used in heat-sensitive adhesive compositions include, for example, the 12th edition of "Compiler Handbook" published by Kobunshi Publishing Association (published in 1055).
These are basically polyvinyl acetate, polybutyl methacrylate, vinyl chloride-vinylidene chloride copolymer, synthetic rubber, vinyl acetate-2-ethylhexyl acrylate copolymer, vinegar ['ni-ethylene copolymer,
Vinylpyrrolidone-styrene copolymer, styrene-7
Polymers such as tadiene copolymer, vinylpyrrolidone-ethyl acrylate copolymer, dicyclohexyl heptatalate, diphenyl phthalate, dihexyl heptathalate, dihydroabietinopeisophthalate dimethyl phthalate, sucrose benzoate, Ethylene glycol dibenzoate, trimethylolethane tribenzoate, tribenzoic acid lyceride, pentaerythritol tetrabenzoate, sucrose helacetate, tricyclohexyl citrate, N-cyclohexyl-p-toluenesulfonamide , dehydroabiethylamine charcoal 1!12 salt, methoxyethyl stearate-urea complex, and a solid plasticizer, and preferably further includes inten resin, ethyl cellulose, petroleum resin (hydrocarbon resin), terpene resin, rosin derivative (polymerized rosin, hydrogenated rosin, pentaerythritol ester of rosin, resin acid dimer, etc.).

According to these descriptions and other known documents, a heat-sensitive adhesive composition can be obtained on a trial basis, but the present inventor has found that it is difficult to obtain a composition that can be put to practical use.

Among the chemical materials mentioned above, the polymer is the source of adhesion, and without it, cohesive force during adhesion cannot be obtained. The solid plasticizer does not impart plasticity to the polymer at room temperature, and therefore the composition is non-adhesive at room temperature, but upon heating, it first melts into a liquid state and swells or dissolves the polymer, causing it to soften or become sticky. to develop tackiness. At this time, if a tackifier is present, the tackiness becomes even more pronounced, and the practical usefulness becomes apparent.

The composition activated by heating is required to maintain its tackiness even after being removed from the heat source and returning to room temperature.

This is because if time is taken from heat activation to application of the adhesive sheet to the adherend, assembly work can be carried out continuously and is very efficient.

(0) Problems to be Solved by the Invention Among the various adherend materials, especially in the case of materials with low polarity such as plastic materials, it is thought that the adhesive remains mainly due to adhesiveness for a certain period of time after application. If the adhesive sheet loses its properties, it may peel off from the adherend prematurely.
This will significantly impair practical value.

The inventor of the present invention has learned from experiments during electric power transformation that this adhesive persistence (duration) is highly dependent on the type of plasticizer, and that even the best of the conventionally known plasticizers does not reach a fully satisfactory level. I learned that there isn't one. Moreover, the pressure-sensitive adhesive sheet before heat activation has the disadvantage that it is likely to cause sticking during storage.

The present invention therefore aims to solve the problem of the prior art in that the duration of viscosity and adhesion after heat activation of heat-sensitive adhesive compositions is not long enough. This aims to improve the blocking properties of adhesive sheets during storage.

In other words, when the above-mentioned heat-sensitive adhesive sheets are rolled up in a roll or stacked in sheets and rolled, a so-called blocking phenomenon may occur where the sheets stick together. The novel plasticizer of the invention can also improve these problems.

Furthermore, it is an object of the present invention to provide a new plasticizer, regardless of whether it is in a liquid or solid state at room temperature, and mainly to contribute to the development of polymerization technology.

(D) Means for Solving the Problems In solving the above problems, the present inventors have made great progress by researching new materials and using them as plasticizers.

The new plasticizer provided by the present invention is represented by the following general formula n
It is a plasticizer consisting of an ester compound of 2-acyloxy-benzoic acid or its derivatives.

(However, in the formula, R1 is alkyl, halogenated alkyl, cycloalkyl, alkenyl, aralkyl (the aromatic ring may have a substituent), aryl (the aromatic ring may have a substituent) a group selected from the group consisting of R7
is a group selected from the group consisting of alkyl, cycloalkyl, aralkyl (the aromatic ring may have a substituent), and aryl (the aromatic ring may have a substituent).

represents a group selected from the group consisting of alkyl, aryl, and halogen, and n represents an integer from θ to 4.

) These ester compounds act as plasticizers! There is no literature that describes its use as a solid plasticizer in heat-sensitive adhesive compositions. The present inventors have also found that these structural isomers, 4-acyloxybenzoic acid or its m-isomer ester compound, sometimes do not exhibit an IF plasticizing effect in heat-sensitive pressure-sensitive adhesive sheets.

Table 1 shows representative examples of ester compounds of 2-acyloxybenzoic acid or derivatives thereof, which are newly proposed by the invention.

Table 1 Plasticizer number Chemical structural formula 0 formula% 0,,,o,O-0,H.

0 arrogance 100 0,. yo　e Oh.

Among these compounds, for example, 厖2, 厖4, 厖5, t1
5.7, A, and 11.423 were liquid at room temperature.

MIJ, which is mainly used for polymers, is as useful as or more useful than conventional liquid plasticizers such as 7-tar acid diesters and phosphoric acid triesters.
As mentioned above, those that are solid (crystalline) at room temperature are particularly useful as solid plasticizers for heat-sensitive adhesive compositions.

The ester compounds of 2-7 syloxybenzoic acid or its aliphatic derivatives of the present invention are produced by first esterifying a carboxyl group by reacting salicylic acid or its fatty acid derivative with an alcohol or a phenol (acid catalyst required), and then It can be synthesized by reacting carboxylic acid anhydrides or halides to acylate the hydroxyl group.

All compounds were virtually colorless liquids or solids (crystals).

In addition, these new plasticizers can be used alone for polymers or organic compounds, or they can be used in combination with multiple ones with different chemical structures, or they can be mixed with known plasticizers to give good results. is obtained.

(Odor Example In this example, "1 part" means 1 "t1 part") Example 1 Seven types of plasticizers used in the present invention were taken and first ground as follows. Made with aqueous suspension.

Plasticizer 50 parts Polyvinyl alcohol 3 parts Nonionic activator
Add water to 3 parts to make plasticizer concentration 25%
This was wet-pulverized using a ball mill to make the plasticizer into fine particles.

Next, 5.0 parts (solid content) of styrene-acrylic acid ester copolymer and 5.0 parts (solid content) of vinyl acetate-ethylene copolymer (
Solid content) Rosin ester 2.5
Part (solid content) of the above plasticizer fine particle suspension 16
(solid content) to prepare an aqueous coating liquid with a total solid content of #IJe of 50%.

When these coating liquids were applied to one side of art paper with a basis weight of 80 g/rn'' so that the dry coating was 'f5t209/m'' and dried at room temperature, a non-stick coated paper was obtained. .

These coated papers were heated in a constant temperature chamber at 150℃ for 30 minutes.
It was activated by heating for a second, and the degree of tack immediately thereafter was evaluated by finger contact test.

The results are shown in Table 2.

In the composition of the present invention to which a plasticizer is added, lamination (tack) is noticeably impaired by heating.

! ! 2 Example 2 A heat-sensitive adhesive sheet was prepared in the same manner as in Example 1, selecting the compound of IK 1 5 of the present invention and the known dichlorohexyl phthalate as plasticizers.

All of these were activated by heating at 150° C. for 30 seconds and exhibited sufficient adhesion and adhesion.

In order to examine the blocking properties of the 40 sheets, each coated paper sample was stacked with the back and front sides facing each other and heated at l'F/6.
Place a weight such that j
It was left to stand for a minute, and then the presence or absence of blocking was examined.

In a comparative example in which dicyclohexyl heptalate was used as a plasticizer, it was observed that the sheets stuck together when they were separated from each other, and also made a loud noise.

On the other hand, in the example of the present invention using compound point 15, no sticking was actually observed and there was no total heat sound.

In other words, a clear improvement in blocking was observed.

Example 3 As plasticizers, the compound of //a18 according to the present invention and the known dicyclohexyl 7-talate were selected, and Example 1 was used, respectively.
Pulverize in the same manner as above to obtain fine particles of aqueous suspension solution/
l L/t::.

Then, 10 parts of ethylene-vinyl acetate copolymer emulgene (
Solid content 0 7 talate dicyclohexyl suspense layer 10m (
Solid content) Compound 4; 18 Susbenziol 5 parts (
Same decision) Water was added to 5 parts (solid content) of a polyhydric alcohol ester emulsion of polymerized rosin to prepare an aqueous coating liquid with a total solid content of $1150%.

For comparison, the plasticizer of the present invention was not used at all as a plasticizer.
A water-based coating solution using only 15 parts (solid content) of dicycyl-a-hexyl tarate and the rest was also the same. The coated amount after drying was 20Ii/m'' in both cases.

These sheets were cut into strips, activated by heating at 150° C. for 30 seconds, immediately attached to the body of a plastic bottle, and left at room temperature for two weeks.

After that, I tried to peel off the San7'' Lucito from the plastic bottle with my fingernail.

As a result, is it possible to invent this invention? The base paper was torn during JJt (base material destruction). On the other hand, the comparative sample was relatively easily peeled off from the interface with the bottle (interfacial failure).

That is, in the example according to the present invention, a clear improvement in the adhesion property was observed.

(Advantageous Effects of the Invention As mentioned above, the present invention mainly provides a new plasticizer that has a remarkable plasticizing effect on polymers, especially those that are solid at room temperature (usually crystalline solid). It is particularly useful as an essential component in heat-sensitive adhesive sheets.

In addition, it is possible to bring about a clear improvement over known products in terms of blocking properties, which is a practical property of heat-sensitive adhesive sheets that not only show remarkable adhesion properties when heated, but also to devise ways to use them. This makes it possible to significantly improve adhesive properties.

Claims (1)

[Scope of Claims] 1. A plasticizer consisting of an ester compound of 2-acyloxy-benzoic acid or a derivative thereof, represented by the following general formula. General formula: ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (However, in the formula, R_1 is alkyl, halogenated alkyl,
A group selected from the group consisting of cycloalkyl, alkenyl, aralkyl (the aromatic ring may have a substituent), and aryl (the aromatic ring may have a substituent), a group selected from the group consisting of alkyl, aralkyl (the aromatic ring thereof may have a substituent), and aryl (the aromatic ring may have a substituent), R_3 is alkyl, aryl, and halogen; n represents an integer from 0 to 4, respectively. )