JPH01126389A - Releasable treatment agent - Google Patents

Abstract

PURPOSE:To obtain a treatment agent for thermoplastic resin film, bakable at a low temperature and capable of forming a face writable with a pen, etc., and having moderate releasability, on any substrate, by using a resin having siloxane segment in the main chain as a component. CONSTITUTION:The objective treatment agent is composed mainly of a solution produced by dissolving (A) a resin selected from polyurethane, polyurea, polyamide and polyester resins having siloxane segment in the main chain in (B) an organic solvent (preferably methyl ethyl ketone, methyl formate, ethyl acetate, etc.) and, as necessary, contains a releasing substance.

Description

Detailed Description of the Invention (Field of Industrial Application) The present invention relates to a releasable treatment agent, and more specifically, it is used in products using adhesives such as adhesive tapes, adhesive labels, adhesive sheets, etc. The present invention relates to a releasable treatment agent that can make the back surface of a base material such as a tape or the surface of a release paper releasable.

(Prior Art) Conventionally, as release agents used for the above purpose, polymer compounds such as acrylic acid, polyester, and polyamide compounds with long-chain alkyl groups bonded to them and organopolysiloxane compounds have been known. It is used to form a release surface on the back of an adhesive tape or adhesive sheet or on the surface of release paper.

Among these, organopolysiloxane compounds have excellent properties such as releasability and residual adhesion.

(Problems to be Solved by the Invention) Although conventional organopolysiloxane compounds have the above properties, they do not have adequate peeling force, and require high temperature baking when coating on a base material. There was a problem that it could not be used for material films. Further, depending on the base material, the adhesion to the base material is insufficient, and there is a drawback that it cannot be used for many types of base materials.

Furthermore, because the critical surface tension of removable polysiloxane compounds is small, it is impossible to write on the releasable surface, and when pressure-sensitive or heat-sensitive adhesives are applied to the releasable surface, they often repel and develop. However, there was a problem that a good coating surface could not be formed.

Therefore, an object of the present invention is to provide a releasable treatment agent that can be baked at low temperatures and can be applied to thermoplastic resin films and the like.

Another object of the present invention is to have no selectivity to the base material;
An object of the present invention is to provide a releasable treatment agent capable of forming a releasable surface on any base material.

Still another object of the present invention is to provide a releasable treatment agent that can form a releasable surface on which writing can be done with water-based ink or oil-based ink.

(Means for solving problems) The above objects are achieved by the present invention as described below.

That is, the present invention is a releasable treatment agent characterized by containing a resin having a siloxane segment in its main chain.

(Function) By using a resin having a siloxane segment in the main chain, it is possible to form a release surface that can be baked at low temperatures, has no selectivity to the base material, is writable with a pen, etc., and has an appropriate release force. .

(Preferred Embodiments) Next, the present invention will be described in more detail by citing preferred embodiments.

The resin having a siloxane segment used in the present invention refers to a resin having two or more reactive groups in the molecule, such as an amino group,
It is obtained by copolymerizing a siloxane compound having an epoxy group, a hydroxyl group, a mercapto group, a carboxyl group, etc. as a type of monomer with other monomers.

For example, the following resins are preferably used.

(+) When the reactive group is an amino group, a polyamide resin obtained by condensation polymerization with a polyhydric carboxylic acid using the amino group.

(2) When the reactive group is a hydroxyl group or a carboxyl group, a polyester resin obtained by condensation polymerization with a polyhydric carboxylic acid or a polyhydric alcohol using the hydroxyl group or carboxyl group.

(3) When the reactive group is a hydroxyl group, a polyurethane resin obtained by addition polymerization with an organic polyisocyanate using the hydroxyl group.

(4) When the reactive group is an amino group, a polyurea resin obtained by addition polymerization with an organic polyisocyanate using the amino group.

(5) A polyurethane polyurea resin obtained by addition-polymerizing an organic polyisocyanate and a combination of a reactive group having an amino group and a reactive group having a hydroxyl group.

As the reactive polysiloxane compound used in the synthesis of the above-mentioned various resins, any conventionally known compound can be used, and preferred examples include the following compounds.

(1) Amino-modified silicone oil (m-〇 to 200) (2) Epoxy-modified silicone oil (n-1 to 200) (Rho 1 to 200) (3) Alcohol-modified silicone oil (n-1 to 2)
00) (m-0 to 50, n”o to 200) (1=1 to 1
01m-10 to 200, n-1 to 5) (4) Carboxyl-modified silicone oil (0-1 to 200) The polysiloxane compound having the above reactive group is
These are examples of preferred compounds in the present invention, and the present invention is not limited to these examples. The above-mentioned exemplified compounds and other compounds are currently commercially available.
Any of these can be easily obtained manually from the market, and any of them can be used in the present invention.

Furthermore, an intermediate obtained by reacting a reactive compound as described above and a polyisocyanate as described below such that at least one of the reactive group of the polysiloxane compound or the isocyanate group of the polyisocyanate group remains, for example, 2
An intermediate obtained by reacting a functional polysiloxane compound and a polyfunctional polyisocyanate in a state rich in isocyanate groups, or conversely, in a state in which a polysiloxane compound is rich in reactive groups, can also be used.

Furthermore, when the reactive group of the polysiloxane compound is a hydroxyl group, an amino group, a carboxyl group, an epoxy group, etc., a polyester polyol obtained by reacting with a polyol, a chain extender, or a polyhydric carboxylic acid or a polyhydric amine described below, Polyamide polyamines, polyether polyols, etc. can also be used in the same manner.

Among the various resins having polysiloxane bonds as described above, particularly preferred in the present invention are those described in (3) above.
These are the polyurethane resins and/or polyurea resins of (5) to (5), and will be explained in more detail using polyurethane resins as a representative example.

The polyurethane resin having a siloxane segment in the main chain is preferably used as all or part of the polyol or chain extension side when preparing a polyurethane resin by reacting a polyol, a polyisocyanate, and a chain extender. It is obtained by using a reactive polysiloxane compound such as.

As the polyol, any conventionally known polyol for polyurethane can be used. For example, it is preferable that the terminal group is a hydroxyl group and the molecular weight is 300 to 4,000.
polyethylene adipate, polyethylene propylene adipate, polyethylene butylene adipate, polydiethylene adipate, polybutylene adipate, polyethylene succinate, polybutylene succinate, polyethylene sebacate, polybutylene sebacate, polytetramethylene ether glycol, poly-C- Examples include caprolactone diol, polyhexamethylene adipate, carbonate polyol, polypropylene glycol, and those containing an appropriate amount of polyoxyethylene chains in the above polyols.

Any conventionally known organic polyisocyanate can be used, but for example, 4,4'-diphenylmethane diisocyanate (MDI) is preferred.
), water-added MDI, isophorone diisocyanate, 1.3-xylylene diisocyanate, 1.4-xylylene diisocyanate, 2.4-tolylene diisocyanate, 2.6-tolylene diisocyanate, 1.5-naphthalene diisocyanate, m- Examples include phenylene diisocyanate, p-phenylene diisocyanate, and urethane prepolymers obtained by reacting these organic polyisocyanates with low molecular weight polyols or polyamines to form terminal isocyanates.

As the chain extender, any conventionally known chain extender can be used; for example, preferred ones include ethylene glycol, propylene glycol, diethylene glycol, 1,4-butanediol, 1,6-hexanediol, ethylenediamine, 1. Examples include 2-propylene diamine, trimethylene diamine, tetramethylene diamine, hexamethylene diamine, decamethylene diamine, decamethylene diamine, isophorone diamine, m-xylylene diamine, hydrazine, and water.

Any polyurethane resin containing a polysiloxane segment in the main chain obtained from the above-mentioned materials can be used in the present invention, but preferably a polyurethane resin in which the polysiloxane segment accounts for about 0.2 to 70% by weight in the resin. If the content of the polysiloxane segment is less than about 0.2% by weight, the desired U effect of the present invention will not be achieved sufficiently, and if the content exceeds about 70% by weight, the adhesiveness to the substrate may deteriorate. This is not desirable as it causes problems.

Incidentally, the polyurea resin and the polyurethane polyurea resin can be obtained in the same manner as described above by using a polyamine in place of all or part of the polyol, or by using a polysiloxane polyamine as the reactive polysiloxane.

Further, preferred ones have a molecular weight of 20,000 to 500,000, and most preferred ones have a molecular weight of 20,000 to 250,000.

The above polysiloxane segment-containing polyurethane resin can be easily obtained by conventionally known manufacturing methods. These polyurethane resins may be prepared without a solvent or in an organic solvent, but in terms of the process, by preparing them in an organic solvent where a stripping agent should be prepared, they can be prepared as is. This is advantageous because it can be used to prepare a strippable treatment agent.

Preferred organic solvents include methyl ethyl ketone, methyl-n-propyl ketone, methyl isobutyl ketone, diethyl ketone, methyl formate, ethyl formate, propyl formate, methyl acetate, ethyl acetate, butyl acetate, and acetone. , cyclohexane, tetrahydrofuran, dioxane, methanol, ethanol, isopropyl alcohol, butanol, toluene, xylene, dimethylformamide, dimethyl sulfoxide, perchloroethylene, trichlorethylene, methyl cellosolve, butyl cellosolve, cellosolve acetate, etc. can also be used. Of course, the above organic solvents can also be used as mixed organic solvents.

By preparing a polyurethane resin in such an organic solvent, a polyurethane resin solution having polysiloxane segments can be obtained, but the solid content can be increased to about 5 to 60% by weight by adding or removing the same or other solvents. It is convenient to have a range. In the present invention, the polyurethane resin may be sufficiently dissolved in an organic solvent, or may be a dispersion in which it is partially or completely precipitated (hereinafter simply referred to as a solution).

The above-mentioned polyurethane resin solution itself is the stripping agent of the present invention, and can be used as it is, and may also be supplemented with various additives such as colorants, crosslinking agents, stabilizers, fillers, etc. can be added arbitrarily.

In particular, as a type of additive, conventionally known mold release substances such as wood flour, talc, silica, boron nitride, alumina, polyethylene resin powder, penzoguanamine resin powder, silicone resin powder, melamine resin powder, fluororesin powder , phenolic resin powder, etc. may be added in an amount of O and 200 parts by weight per 100 parts by weight of the siloxane segment-containing resin.

Furthermore, general thermoplastic or thermosetting resins can also be used as additives.

(Effects) According to the present invention as described above, by using a resin having a siloxane segment in the main chain, it can be baked at a low temperature, has no selectivity to the base material, can be written on with a pen, etc., and has an appropriate peeling force. It is possible to form a peeling surface having the following properties.

Next, the present invention will be specifically explained with reference to Examples and Comparative Examples. It should be noted that unless otherwise specified, the terms in the text or % are based on weight.

Example 1 (Synthesis of polyurea resin) II I C) 13 C83CH3 (n is a value giving an average molecular weight of 3,880) Dimethyl polysiloxane diamine of the above formula (average molecular weight 3,
880) 150 parts and 1,3-propylenediamine
0 parts were added to 250 parts of dimethylformamide, and the mixture was charged into a reactor equipped with a stirrer, a reflux condenser, a dropping funnel, and a gas inlet tube. The contents are externally cooled to a temperature of 0 to -5°C, and carbon dioxide gas is continued to flow through the gas introduction pipe while maintaining this temperature.

Next, a solution of 15 parts of water-added MDI dissolved in 65 parts of dimethylformamide was dropped into the reactor through the dropping funnel to cause a reaction. After the dropping was completed, the internal temperature was gradually raised, and when it reached 50°C, stirring was continued at 50°C for 1 hour.

The resulting polyurea resin solution had a solids content of 35% and a viscosity of 15.0OOcps (25°C).

The breaking strength of the film formed from this solution (Kg/cr
rI″) at 450°C, elongation at break (%) at 550°C,
Moreover, the softening point was 150°C or higher.

Example 2 (Synthesis of polyurea resin) 150 parts of the polysiloxane diamine in Example 1 having an average molecular weight of about 1,000 were added to a mixed organic solvent consisting of 100 parts of dimethylformamide and 150 parts of methyl ethyl ketone, Also, 39 parts of water added MDI
A polyurea resin solution was obtained in the same manner as in Example 1 except that 100 parts of methyl ethyl ketone was used.

The solids content of this solution was 35% and 10,000 cp
s (25°C).

The breaking strength of the film formed from this solution (in g/c
rn”) is 210°C, and the elongation at break (%) is 650°C.
And the softening point was 150°C or higher.

Example 3 (Synthesis of polyurethane resin) C1la CH3(:H3 (n is a value giving an average molecular weight of 3,200) Polydimethylsiloxane diol represented by the above formula and having an average molecular weight of about 3.200 150 parts and 10 parts of 1,4-butanediol were added to a mixed organic solvent consisting of 200 parts of methyl ethyl ketone and 50 parts of dimethyl formamide, and a solution of 40' part of water-added MDI dissolved in methyl ethyl ketone was used. However, a polyurethane resin solution having siloxane bonds was obtained in the same manner as in Example 1.

The solids content of this solution was 35% and 14,700 cp
s (25°C).

The breaking strength (in g/C) of the film formed from this solution was 200°C, the breaking elongation (%) was 560°C, and the softening point was 100°C or less.

Example 4 (synthesis of polyurethane resin) Same structure as Example 3, but with an average molecular weight of about 1.000
150 parts of polydimethylsiloxane diol was dissolved in 250 parts of methyl ethyl ketone, and 39 parts of water was added.
A polyurethane resin solution having siloxane bonds was obtained in the same manner as in Example 1 except that DI was dissolved in 100 parts of methyl ethyl ketone.

The solids content of this solution was 35% and 11,600 cp
s (25°C).

The breaking strength of the film formed from this solution (in g/cr
n'') was 90°C, elongation at break (%) was 700°C, and softening point was 100°C or less.

Comparative Example 1 (Synthesis of conventionally known polyurethane resin) A mixture of 150 parts of polybutylene adipate having an average molecular weight of about 2,000 and 10 parts of 1,4-butanediol with 120 parts of methyl ethyl ketone and 130 parts of dimethylformamide. Dissolved in an organic solvent and also added 47 parts of water MD
A polyurethane resin solution was obtained in the same manner as in Example 1 except that I was dissolved in 135 parts of methyl ethyl ketone.

The solids content of this solution was 35% and 14,500 cp
s (25°C).

The breaking strength of the film formed from this solution (Kg/c
rn”) is 250℃, and the elongation at break (%) is 500℃.
And the softening point was 100°C or less.

Comparative Example 2 Polysiloxane resin (product name: NiS) manufactured by Shin-Etsu Chemical Co., Ltd.
-841) 100 parts and the accompanying solution (product name;
PL-7) 1 part and dissolved in 1,000 parts of toluene,
A coating liquid of polysiloxane resin was used.

Examples 5 to 8 and Comparative Examples 3 to 4 The following release treatment agents were added to 100% modulus of 60 g/c.
A sample with a releasable coating layer was obtained by uniformly coating one side of a polyvinyl chloride film with a thickness of 50 μm with rrI'' at a coating amount of 0.6 g/m'' solid content, and heating and drying at 80° C. for 30 seconds. It was created. Note that when the temperature was raised to a high temperature (100° C. or higher), the polyvinyl chloride film softened and could not maintain its shape as a film.

Acrylic adhesive tape (manufactured by Miki Kagaku) with a width of 20 mm was pressed onto the coated substrate prepared in this way using a rubber roller weighing 2 g, and after one day at room temperature (20 °C, humidity 52%) and at high temperature (40 °C). Peeling force after being left for 3 days at (℃, humidity 90% or higher)
The residual adhesive strength, residual adhesive strength retention rate, shedding property of the releasable coating layer, and writability with magic ink were measured, and the results are shown in Table 1 below.

X side 1 Resin solution of Example 1 100 parts Methyl ethyl ketone 250 parts Side Resin solution of Example 2 100 parts Fluororesin powder (Daikin Industries Nilbrone L-2),
5 parts methyl ethyl ketone
250 parts 9 cases U Resin solution of Example 3 100 parts Coronate L (adduct of trimethylolpropane and TDT)
2 parts methyl ethyl ketone
250 parts mixed 1 100 parts of the resin solution of Example 4 Coronated 2 parts silicone resin powder (
Toshiba Silicone, Tosvaal 120)
5 parts methyl ethyl ketone 25
0 parts Resin solution of Comparative Example 1 100 parts Silicone oil (SH-200, Toshi Silicone)
5 parts methyl ethyl ketone
250 parts Resin solution of Pattern Example A Comparative Example 2 100 parts Each evaluation was performed in accordance with the following.

Peeling force: A 20 mm wide adhesive tape was attached to the peelable film layer, and after being stored for 24 hours at 40°C and a load of 20 g/crn', it was peeled off at 300 m.
The sample was pulled at an angle of 180° at a speed of m7 minutes, and the force (g) required for peeling was measured (20°C).

Residual adhesive strength: After measuring the peeling force, the adhesive tape was attached to a #280 stainless steel plate, passed through a 2-g tape roller once, and after 30 minutes, pulled at a speed of 300 mm and 7 minutes at an angle of 180° and peeled off. The force (g) required to do so was measured (20°C).

Residual adhesive strength retention rate: A clean adhesive tape was attached to a #280 stainless steel plate without peeling resistance, and the adhesive strength (320g/20n++++) to the stainless steel plate was 100%.
It shows the percentage of residual adhesive strength when

Shedding property: A peelability test of the peelable film layer is performed on the sample after the gauze is passed back and forth on the peelable film layer once with a load of 50 g/cm.

Writability with marker ink: Characters were written on the releasable coating layer using a commercially available oil-based marker ink, and the presence or absence of ink repellency during writing was examined.

'7 1 - One fork five ■ - 20III11 Room temperature 1 day later (20℃, 52!ji) 23
18 35 High temperature after 3 days (40℃, over 90)
25 23 380ml Room temperature 1 day later (20℃, 52%) 3 (15'3
11 292 High temperature after 3 days (40℃, over 90)
291 305 280 [After 1 day at room temperature (20℃, 52%) 95 97
91 high temperature 3 days later (40℃, 9096 or higher) 9
1 95 87 Wind-Tangled at room temperature 1 day later (20℃, 52%) ○ O○υ
Sugiyama Yoshimu Color proof after 1 day at room temperature (20℃, 5296) ○ ○
○-20ml11 Room temperature 1 day later (20℃, 52' high temperature 3 days later (40℃, 90* or higher) Effect -20fflI11 Room temperature 1 day later (20℃, 52!K) High W 3 days later (40℃, 90% or higher) - After 1 day at room temperature (20℃, 52%) After 3 days at high temperature (40℃, over 90) After 1 day at room temperature (20℃, 5296)

Claims (4)

[Claims] (1) A releasable treatment agent characterized by containing a resin having a siloxane segment in its main chain. (2) The resin is polyurethane resin, polyurea resin,
The releasable treatment agent according to claim 1, which is selected from the group consisting of polyamide resins and polyester resins. (3) Claim No. (1) further containing a releasable substance
) The releasable treatment agent described in item 2. (4) The stripping treatment agent according to claim (1), which is an organic solvent solution.