JP2980874B2 - Removable antistatic protective adhesive film - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a liquid crystal panel and a CR.
The present invention relates to an antistatic protective film made of a removable pressure-sensitive adhesive sheet or tape having an antistatic function used to protect the surface of a T (CRT) or the like during production, transportation, and storage thereof. is there.

[0002]

2. Description of the Related Art Removable protective adhesive sheets made of synthetic resin to prevent scratches, adhesion of dust, contamination and the like during the production and transportation of liquid crystal panels such as personal computers, word processors, calculators and CRTs. Alternatively, a protective adhesive tape is stuck on a liquid crystal panel or a CRT surface to protect the tape. However, when the conventional protective sheet or protective tape has finished its role of protecting the liquid crystal panel surface and the like and then peels off from the panel surface and the like, static electricity is generated, and as a result, the IC of the circuit is destroyed, and dust or dust is generated on the panel surface. Since troubles such as adhesion sometimes occur, the following measures have been taken to avoid such troubles.

[0003] A protective sheet or tape in which a surfactant is kneaded with a base material and / or an adhesive is used. A protective sheet or tape mixed with a conductive filler such as carbon black is used. A protective sheet or tape in which a resin such as conductivity or hydrophilicity is kneaded is used. Use a static eliminator or the like.

However, of the above-mentioned trouble avoiding means,
When the surfactant is kneaded, the antistatic effect is insufficient, the influence of humidity is large and it is unstable, and the characteristics of the adhesive change when the surfactant bleeds out to the adhesive Glue residue is likely to occur,
Surfactants that are more likely to contaminate the adherend even if no glue residue occurs are gradual, but many still have to be solved, such as volatilization in the air and loss of the antistatic effect. There is a problem.

[0005] In addition, those obtained by kneading the conductive filler have poor transparency, making it difficult to confirm the surface of the adherend with the protective sheet adhered thereto.
In the case of using a mixture of resins such as hydrophilicity, the compatibility with the base material and the resin to be used as the adhesive is often poor, and it is not dispersed well, so the antistatic effect is not high. Has a limited static elimination capability, so that the speed of attaching the protective sheet cannot be increased, and a static eliminator or the like is required even when the protective sheet is peeled off, which limits the working place (environment) ( If it is peeled off where there is no equipment, static electricity will be generated).

[0006]

SUMMARY OF THE INVENTION Therefore, the present invention can solve the above-mentioned problems of the conventional antistatic protective film, is excellent in transparency, and generates static electricity during sticking and peeling operations. It does not occur, so there is no destruction of the IC of the circuit due to the charging of the panel surface,
It is another object of the present invention to provide a removable antistatic protection film that does not cause contamination of a panel surface or the like due to dust adhesion or the like due to adhesive residue or the like.

[0007]

According to the present invention, there is provided a pressure-sensitive adhesive layer applied to a synthetic resin sheet or tape-like film substrate surface. The present invention relates to a removable antistatic protective pressure-sensitive adhesive film comprising a pressure-sensitive adhesive layer containing a resin having excellent transparency.

In particular, according to the present invention, the resin contained in the base material or in both the base material and the pressure-sensitive adhesive layer may be one or two resins selected from the resins comprising a repeating unit represented by the following general formula (1).
Kind Code: A1 The present invention relates to a removable antistatic protective pressure-sensitive adhesive film characterized by being at least one kind. - [YXYR _2] - in ..... (1), Y is - [CH ₂ CH ₂ O] - and - [CH ₂ CH
(R ₁ ) O]-is a unit composed of repeating units.
However, in Y - [CH ₂ CH ₂ O] - 70 wt%
There above, - [CH ₂ CH ₂ O] - repeat number of a positive number. Further, the number of repetitions of-[CH ₂ CH (R ₁ ) O]-is 0 or a positive number. R ₁ is a hydrocarbon group. X is an organic compound residue having two active hydrogen groups. R ₂ is a dicarboxylic acid compound residue or a diisocyanate compound residue.

The present invention further relates to a water-soluble resin of the general formula (1), wherein one or two or more compounds selected from compounds having a weight average molecular weight of 50,000 or more obtained by reacting the following components (A) and (B): The present invention relates to a removable antistatic protective pressure-sensitive adhesive film characterized by using the following. (A): a polyoxyalkylene polyol having a weight average molecular weight of 1000 or more, obtained by addition-polymerizing an alkylene oxide containing 70% by weight or more of ethylene oxide to a compound having two active hydrogen groups. (B): at least one of dicarboxylic acid compounds and diisocyanate compounds.

Further, the present invention comprises a synthetic resin film substrate having excellent transparency and a removable pressure-sensitive adhesive layer applied to the film substrate surface, wherein the substrate and / or the pressure-sensitive adhesive layer are A water-soluble resin that does not impair the transparency as the protective adhesive film, 1 to 100 parts by weight of the water-soluble resin, preferably 5 to 100 parts by weight of the base material and / or the adhesive.
The present invention relates to a removable antistatic protective pressure-sensitive adhesive film which is added and contained in a proportion of 50 parts by weight, more preferably 10 to 40 parts by weight.

In the present invention, the pressure-sensitive adhesive is selected from acrylic, ethylene-vinyl acetate copolymer, ethylene-acrylate ester, styrene-isoprene block copolymer, and styrene-butadiene block copolymer. The present invention relates to a removable antistatic protective pressure-sensitive adhesive film characterized by one or more types.

The film substrate used for the sheet- or tape-shaped pressure-sensitive adhesive film of the present invention is polyethylene, polypropylene, polyester, polyvinyl chloride, polyamide, ethylene / propylene copolymer, polystyrene, polycarbonate, polyurethane, polyacetal, etc. And especially a film made of a thermoplastic resin that can be formed into a film by a melt extrusion method. The synthetic resin substrate preferably has a thickness of 10 μm to 100 μm. If it is less than 10 μm, the protective function of the panel surface or the like is not sufficient, and if it exceeds 100 μm, it is not preferable because it lacks flexibility and the shape followability decreases.

The pressure-sensitive adhesive used for the pressure-sensitive adhesive sheet or tape of the present invention has a characteristic that it can be removably adhered to a surface of a liquid crystal panel or the like without leaving any adhesive, and has a property of improving the transparency of the entire sheet or tape. There is no particular limitation as long as it does not impair, but for example, acrylic, EVA (ethylene-vinyl acetate copolymer), EEA (ethylene-acrylate copolymer), SIS (styrene-isoprene block) Those which can be formed into a film by a melt extrusion method, such as a copolymer), a hot melt type, an SBS (styrene-butadiene block copolymer) type and the like are preferable. The pressure-sensitive adhesive is preferably applied to the substrate surface as a layer having a thickness of 3 to 50 μm in order to form a removable pressure-sensitive adhesive layer.

The water-soluble resin added to the synthetic resin film substrate and / or the pressure-sensitive adhesive layer of the present invention is compatible with the substrate and the pressure-sensitive adhesive, and adversely affects the adhesion and removability of the pressure-sensitive adhesive layer. Without, those that do not impair their transparency are preferred,
A water-soluble polymer compound having a weight average molecular weight of 50,000 or more and composed of a repeating unit represented by the following general formula (1) is preferable.

-[YXYR ₂ ]-(1) wherein Y is-[CH ₂ CH ₂ O]-and-[CH ₂ C
H (R ₁ ) O]-. However, in the Y - [CH ₂ CH ₂ O] - it is present more than 70 wt%, - [CH ₂ CH ₂ O] - repeat number of a positive number. The number of repetitions of-[CH ₂ CH (R ₁ ) O]-is 0 or a positive number. R ₁ is a hydrocarbon group. X is an organic compound residue having two active hydrogen groups. R ₂ is a residue of a dicarboxylic acid compound or a residue of a diisocyanate compound. ]

The water-soluble polymer compound composed of the repeating unit represented by the general formula (1) has a weight average molecular weight of 500 obtained by reacting the following components A and B:
It is a polymer compound of 00 or more. (A): a polyoxyalkylene polyol having a weight average molecular weight of 1000 or more, obtained by addition-polymerizing an alkylene oxide containing 70% by weight or more of ethylene oxide to a compound having two active hydrogen groups. (B): at least one of dicarboxylic acid compounds and diisocyanate compounds.

Examples of the compound having two active hydrogen groups in the component A used in the above reaction include ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, 1,4-butanediol,
Alicyclic diols such as 6-hexanediol, neopentyl glycol, bisphenol A, polytetramethylene glycol, cyclohexane-1,4-dimethanol,
Examples include amines such as butylamine, octylamine, laurylamine, cyclohexylamine, and aniline.

Examples of the alkylene oxide containing 70% by weight or more of ethylene oxide which can be used for producing the component A used in the above reaction include ethylene oxide alone, propylene oxide containing 70% by weight or more of ethylene oxide, butylene oxide, styrene oxide and the like. Alkylene oxide mixtures are mentioned. If ethylene oxide is less than 70% by weight of the entire alkylene oxide, it tends to be insoluble in water.

The reaction for producing the polyoxyalkylene polyol as the component A is carried out by adding a compound having two active hydrogen groups to an alkylene oxide containing at least 70% by weight of ethylene oxide, for example, sodium hydroxide, potassium hydroxide or the like. Approximately 90 to 20 using caustic as a catalyst
It can be obtained by block or random addition polymerization at a temperature of 0 ° C. for about 2 to 30 hours. The resulting polyoxyalkylene polyol has a weight average molecular weight of 10
00 or more, preferably 5000 to 30000. If the weight average molecular weight is less than 1,000, the proportion of the corresponding dicarboxylic acid compound or diisocyanate compound added to the linking agent is increased, so that the water solubility tends to deteriorate.

In the component B used in the above reaction, examples of the dicarboxylic acid compound include those described in the following (a), (b) and (c). (A) phthalic acid, isophthalic acid, terephthalic acid, malonic acid, succinic acid, sebacic acid, maleic acid, fumaric acid, adipic acid, itaconic acid, (b) methyl ester, dimethyl ester, ethyl ester, diethyl of (a) Lower alkyl esters such as esters, propyl esters, dipropyl esters, butyl esters, and dibutyl esters; (c) acid anhydrides of (a);

In the component B used in the above reaction, examples of the diisocyanate compound include tolylene diisocyanate, diphenylmethane diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, xylylene diisocyanate, 4,4'-methylene bis-
(Cyclohexyl isocyanate) and the like.

In the reaction for producing a water-soluble polymer compound composed of the repeating unit represented by the general formula (1), in the case of using a dicarboxylic acid compound as the component B, a polyoxyalkylene polyol (A ) Is prepared, and a dicarboxylic acid compound (B) is added thereto.
The temperature is raised, and under heating at 80 to 250 ° C., 0.1 to
Dehydration or de-alcoholization is performed under a reduced pressure of 2.7 × 10 ³ Pa. The reaction time during this period is usually 30 minutes to 10 hours. When the component (A) and the component (B) are allowed to react, the mixing ratio (A / B) of the two is specifically equivalent ratio, A / B = 1 / 0.5 to 1 / 3.5, Preferably, A / B = 1 / 0.95 / 1 / 3.5.

In the reaction using a diisocyanate compound as the component B, that is, in the urethanization reaction with the diisocyanate compound, for example, the blending ratio of the polyoxyalkylene polyol (A) and the diisocyanate compound (B) is adjusted to an NCO / OH equivalent ratio of 0. The mixing is performed within a range of 0.5 to 1.5, and the reaction is performed at a temperature of 80 to 150 ° C. for 1 to 5 hours. The weight average molecular weight of the water-soluble polymer compound thus obtained is preferably set to 50,000 or more, more preferably 10,000.
0 to 300,000.

These water-soluble resins are usually preferably added at a ratio of 1 to 100 parts by weight per 100 parts by weight of the base material or the total of the base material and the adhesive. If the addition ratio is less than 1 part by weight per 100 parts by weight of the base material or the total of the base material and the pressure-sensitive adhesive, the antistatic function may be insufficient.
Even if the amount exceeds 00 parts by weight, no further effect corresponding to the cost increase can be expected.

[0025]

According to the present invention described above, both of the film substrate and the pressure-sensitive adhesive layer are electrically conductive due to the water-retaining property of the water-soluble resin added to the substrate and / or the pressure-sensitive adhesive. There is no charge, and thus the surface of the liquid crystal panel or the like in contact with the pressure-sensitive adhesive layer is not charged when the pressure-sensitive adhesive layer is peeled off. In addition, the water-soluble resin is compatible with the film substrate and the pressure-sensitive adhesive layer even in the film base and the pressure-sensitive adhesive layer without impairing the transparency. If the addition ratio is not more than 10 parts by weight, the adhesion of the pressure-sensitive adhesive layer is not impaired. Furthermore, since a resin that can be hot melt extruded is used as the film base material and pressure-sensitive adhesive resin, the base film and the pressure-sensitive adhesive layer can be laminated in a state where they are firmly bonded to each other by coextrusion. In addition, the adhesive residue of the adhesive can be reduced.

[0026]

EXAMPLES The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples. Example 1 A polyethylene glycol prepared by addition polymerization of ethylene glycol with ethylene oxide alone (ethylene oxide 1
(100%, weight average molecular weight 10,000), 100 parts of dimethyl sebacic acid was added, and a transesterification reaction was performed by a known method to obtain a water-soluble resin (a) having a weight average molecular weight of 150,000. This is because, in the repeating unit represented by the general formula (1), Y, X, and R ₂ are as follows.

Embedded image

LDPE (trade name: F-14, manufactured by Mitsubishi Kasei Corporation)
1) 100 parts by weight of the water-soluble resin (a) 2
A mixture containing 0 parts by weight was used as a base film composition, and EVA (manufactured by Mitsubishi Yuka Co., Ltd .: trade name V-501H) 10
A mixture obtained by mixing 20 parts by weight of the above water-soluble resin A with respect to 0 parts by weight was used as a pressure-sensitive adhesive composition, and the two-layer extrusion method using a T-die was used. A removable antistatic pressure-sensitive adhesive film was produced so as to have a thickness of 15 μm. The properties shown in Table 1 were evaluated for this removable antistatic pressure-sensitive adhesive film.

EXAMPLE 2 2.7 parts of dimethyl isophthalate was added to 100 parts of a polyalkylene glycol (85% ethylene oxide, weight average molecular weight of 14,000) obtained by addition polymerization of propylene oxide and ethylene oxide in a block with aniline, followed by addition of ester. Weight average molecular weight 1700 by exchange reaction
00 water-soluble resin (b) was obtained. Y, X, and R ₂ are as follows.

Embedded image A removable antistatic pressure-sensitive adhesive film was produced in the same manner as in Example 1 except that the water-soluble resin (b) was used instead of the water-soluble resin (a) of Example 1. The characteristics were as shown in Table 1.

Example 3 Polyethylene glycol obtained by addition polymerization of ethylene oxide with ethylene glycol alone (ethylene oxide 1
1.9 parts of dimethyl terephthalate was added to 100 parts of a water-soluble resin (c) having a weight average molecular weight of 130,000.
I got Y, X, and R ₂ are as follows.

Embedded image A removable antistatic pressure-sensitive adhesive film was produced in the same manner as in Example 1 except that the above water-soluble resin (c) was used instead of the water-soluble resin (a) in Example 1. The characteristics were as shown in Table 1.

Example 4 Polyethylene glycol obtained by addition polymerization of ethylene glycol and ethylene oxide alone (ethylene oxide 1
(100%, weight average molecular weight 10,000), 1.6 parts of hexamethylene diisocyanate was added, and a urethanation reaction was carried out by a known method to give a weight average molecular weight of 13,000.
0 water-soluble resin (d) was obtained. This is because, in the repeating unit represented by the general formula (1), Y, X, R ₂
Is as follows.

Embedded image A removable antistatic pressure-sensitive adhesive film was produced in the same manner as in Example 1 except that the above water-soluble resin (d) was used instead of the water-soluble resin (a) of Example 1. The characteristics were as shown in Table 1.

Example 5 A polyalkylene glycol obtained by addition-polymerizing ethylene glycol with propylene oxide and ethylene oxide in a block (ethylene oxide 85%, weight average molecular weight 10
000) and 100 parts of 2,4-tolylene diisocyanate (3.1 parts), and a urethanization reaction was carried out by a known method to prepare a water-soluble resin (e) having a weight average molecular weight of 100,000. Y, X, and R ₂ are as follows.

Embedded image A removable antistatic pressure-sensitive adhesive film was produced in the same manner as in Example 1 except that the above water-soluble resin (e) was used instead of the water-soluble resin (a) of Example 1. The characteristics were as shown in Table 1.

Example 6 A water-soluble resin (a) of Example 1 was used, using a polyester film as a base material and 100 parts by weight of a solid content of an acrylic re-peelable pressure-sensitive adhesive (SK Dyne 1473H, manufactured by Soken Chemical Co., Ltd.).
A removable antistatic pressure-sensitive adhesive film was produced by using 20 parts by weight as a pressure-sensitive adhesive composition so that the pressure-sensitive adhesive layer had a thickness of 15 μm. The characteristics were as shown in Table 1.

Comparative Example 1 A removable adhesive film was prepared in the same manner as in Example 1 except that the water-soluble resin (a) was not used. The characteristics were as shown in Table 1. Comparative Example 2 A removable adhesive film was prepared in the same manner as in Example 6, except that the water-soluble resin (a) was not used. The characteristics were as shown in Table 1.

[0034]

[Table 1]

[0035]

As described above in detail, the removable pressure-sensitive adhesive sheet or tape of the present invention protects the display surface of an electronic device such as a liquid crystal panel while maintaining the transparency of a substrate or the like. While excellent in function, even when peeled after finishing the role as a protective sheet or tape because the protective adhesive sheet or tape itself is not charged,
Without charging the display surface of electronic devices,
Therefore, the destruction of electronic components such as ICs due to the charging of the surface portion does not occur.

──────────────────────────────────────────────────続 き Continuation of the front page (72) Inventor Takeshi Fujita 114-9 Ono, Hirono-cho, Uji-city, Kyoto (72) Inventor Chuzo Isoda 64-9, Shinmeimiyakita, Uji-city, Kyoto (56) References JP-A-8 -81658 (JP, A) (58) Fields investigated (Int. Cl. ⁶ , DB name) C09J 7/00-7/04 C09J 11/08 WPI / L (QUESTEL)

Claims (4)

(57) [Claims] 1. A compound having a removable pressure-sensitive adhesive layer on the surface of a synthetic resin film substrate, wherein the substrate or the substrate and the pressure-sensitive adhesive layer comprise a repeating unit represented by the following general formula (1): A removable antistatic protective pressure-sensitive adhesive film comprising one or more water-soluble resins selected from the group consisting of: - [YXYR _2] - ----- (1) wherein, Y is - [CH ₂ CH ₂ O] - and - [CH ₂ C
H (R ₁ ) O]-. However, in Y - [CH ₂ CH ₂ O] - it is present more than 70 wt%, - [CH ₂ CH ₂ O] - repeat number of a positive number. Further,-[CH ₂ CH (R ₁ ) O]-
Is 0 or a positive number. R ₁ is a hydrocarbon group. X is an organic compound residue having two active hydrogen groups. R ₂ is a dicarboxylic acid compound residue or a diisocyanate compound residue. 2. The method according to claim 1, wherein the water-soluble resin is added at a ratio of 1 to 100 parts by weight per 100 parts by weight of the base material or the total amount of the base material and the adhesive. Peelable antistatic protective adhesive film. 3. The water-soluble resin has a weight average molecular weight of 500 obtained by reacting the following compounds (A) and (B).
The removable antistatic protective pressure-sensitive adhesive film according to claim 1, wherein the film is at least one compound selected from 00 or more compounds. (A): a polyoxyalkylene polyol having a weight average molecular weight of 1000 or more, obtained by addition-polymerizing an alkylene oxide containing 70% by weight or more of ethylene oxide to a compound having two active hydrogen groups. (B): at least one of dicarboxylic acid compounds and diisocyanate compounds. 4. The pressure-sensitive adhesive is acrylic, ethylene-vinyl acetate copolymer, ethylene-acrylate,
The re-peelable charging according to any one of claims 1 to 3, wherein the charging is at least one selected from a styrene-isoprene block copolymer system and a styrene-butadiene block copolymer system. Preventive protective adhesive film.