JPH02175779A - Selectively adhering composition and selectively adhering article - Google Patents

Abstract

PURPOSE:To prepare an adhering compsn. which adheres strongly to a flat film but does not adhere to an uneven surface such as that of a non-woven fabric, paper, etc., by compounding a styrene-ethylene-butylene-styrene block copolymer with a tackifier and a liquid resin. CONSTITUTION:100 pts.wt. styrene-ethylene-butylene-styrene block copolymer comprising two phases consisting of terminal styrene block phase and ethylene-butylene rubber phase not contg. a double bond, wherein the MWs of styrene block and ethylene- butylene rubber block are 7000-20000 and 35000-50000, respectively, and the styrene and ethylene-butylene contents are 20-40wt.% and 60-80wt.%, respectively; is compounded with 50-80 pts.wt. tackifier selected from the group consisting of a 5C and/or 9C petroleum resin having a softening point of at least 80 deg.C and an average MW of 400-2000, a polyterpene resin comprising a polymer of alpha-pinene, beta-pinene or dipentene, a rosin-derived resin and hydrogenated products of these resins; 40-70 pts.wt. liquid resin selected from the group consisting of a high-boiling hydrocarbon resin having a softening point of -5 to 10 deg.C and an average MW of 200-7000, a hydrogenated polypentene liquid resin, polyterpene-derived liquid resin and a rosin-derived liquid resin.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to an adhesion selective composition and an adhesion selective article;
In detail, it easily and strongly adheres to flat films such as polypropylene, polyethylene, and polyester with a slight pressure, but it does not really adhere to highly uneven surfaces such as nonwoven fabrics and paper due to its low tackiness, and it does not adhere for long periods at high temperatures. The present invention relates to an adhesion selective composition and an adhesion selective article that adhere only to the extent that it can be easily peeled off by hand even when pressed.

[Conventional technology]

Self-adhesive or self-adhesive compositions and articles are known as adhesive selective compositions and articles that adhere only to specific locations. In other words, the coating surfaces formed by self-adhesive or self-adhesive compositions easily adhere strongly (adhere) to each other with a slight pressure; It does not indicate gender.

Such self-adhesive or self-adhesive compositions and articles are disclosed in JP-A-55-106275 and JP-A-60-26.
Those described in Japanese Patent Laid-open No. 077 and Japanese Unexamined Patent Publication No. 62-66825 are known.

In addition, as a selective bonding method, JP-A-61-141196, JP-A-61-172397, JP-A-61-
No. 221123 and Japanese Unexamined Patent Publication No. 61-233354 are known. JP-A-54-58734 is known as relating to both self-adhesive articles and adhesive selection methods. In addition, JP-A-54-56636, JP-A-58-501-863, and JP-A-62-19 have compositions similar to the adhesion selective composition of the present invention.
No. 7481 is known.

To explain the conventional techniques described in the above-mentioned publications regarding self-adhesive or self-adhesive compositions, JP-A-55
-106275 publication describes natural rubber and polystyrene-
A self-produced adhesive composition containing a polyisoprene-polystyrene copolymer as an adhesive component is described. Furthermore, in JP-A No. 60-26077, an aqueous solution containing a uniform mixture of rubber latex and a water-soluble adhesive is coated and dried on the surface of a tape-shaped base material, and then the dried coating surface is coated with an anti-blocking agent. A self-adhesive tape is described that is processed by. Furthermore, JP-A No. 62-66825 discloses a structure in which a plurality of adhesive sheets each consisting of a support and a pressure-sensitive adhesive layer are laminated, and the main component of the pressure-sensitive adhesive layer is a styrene-ethylene-butylene-styrene plotter copolymer. A laminated mat consisting of a combination is described.

To explain the conventional technique described in the above-mentioned publication regarding the selective adhesion method, Japanese Patent Laid-Open No. 141196/1983 discloses that a part of the conductive pattern is exposed, the other part is masked with tape, and then resin adhesive is applied. A method is described in which the adhesive is immersed in an electrodeposition bath containing an adhesive, and the adhesive is applied only to the exposed portions for selective adhesion. Also, JP-A-61
-172397 discloses that a conductive adhesive layer is formed on a substrate, this is semi-cured, another adhesive layer is formed, and the other substrate is pressure bonded to this under heat. A method is described in which only selected portions of a conductive pattern are adhered to each other while maintaining the reliability of the adhesive layer. Also,
JP-A No. 61-221123 discloses that a solid having a fluorine-containing segmented 20 surface is used as a material for separating lymphocytes, and B cells are selectively adhered to the solid by contacting with a lymphocyte-containing liquid, thereby separating lymphocytes. A method for efficiently separating the is described. Furthermore, Japanese Patent Application Laid-Open No. 61-233354 discloses that cells can be bonded by using a working bridge whose electrode potential is controlled based on the potential of a saturated Carmelo electrode, which is a reference electrode, as a material for selectively adhering cells. A method for separation in a short period of time without damage and with a high recovery rate is described.

To explain the conventional techniques described in the above-mentioned publications regarding both self-adhesive substances and adhesive selection methods, Japanese Patent Laid-Open No. 54-58734 discloses a method of using a plastic foam having a cellular structure as an open cell surface layer. A material is described in which an acrylic adhesive is applied to the side walls inside the cell, and only when pressure is applied, the side walls coated with the adhesive are exposed to the surface of the adherend, resulting in selective bonding.

To explain the conventional technology described in the above-mentioned publication regarding compositions similar to the adhesion selective composition of the present invention, JP-A-54-56636 discloses styrene-ethylene-butylene-styrene (hereinafter referred to as Hydrogenated block polymers such as 5EBS) and styrene-ethylene-propylene-styrene (5EPS)
0 parts by weight to 50 parts by weight of tackifier resin miscible in the rubber phase.
~200 parts by weight, or 10 parts by weight of a resin miscible with the styrene phase
~200 parts by weight, paraffin, naphthenic oil 0-2
00 parts by weight, and 1 to 100 parts by weight of the polyphenylene ether resin featured in this publication at 230 to 260°C.
A hot melt adhesive composition is described which is kneaded with. JP-A No. 58-501863 discloses that 50 to 150 parts by weight of a petroleum-based or polyterpene-based tackifier,
25-200 parts by weight of polybutene or polyisobutylene, 1-25 parts by weight of oil optionally containing 2% by weight of polar compounds, 1-150 parts by weight of fillers such as calcium carbonate, silica, etc.
Adhesive compositions are described in which parts by weight are dissolved in a solvent. JP-A-62-197481 discloses an ABA or ABAB type non-elastomer polymer block (A
) is styrene, and the elastomer block (B) is butadiene or hydrogenated butadiene. Block polymer 20
~35% by weight, 45-70% by weight of tackifiers of ordinary natural or petroleum origin or hydrogenated derivatives thereof, 5-3% by weight of softeners.
A hot melt adhesive composition for manufacturing Honkawa cases is described in which 0% by weight is kneaded at 130 to 200° C. for 2 hours.

[Problems to be Solved by the Invention] The conventional techniques related to the above-mentioned self-adhesive substances had the following problems.

JP-A No. 55-106275, JP-A No. 60-260
Self-adhesive compositions, including Publication No. 77, exhibit adhesion only between coating surfaces formed of the same composition or similar compositions, and do not adhere to other articles, so it is difficult to adhere them to a support. Both parts must be coated with the same or similar composition. Since the application of self-adhesive substances is mainly carried out using a solvent or emulsion system, problems arise such as the need for solvent removal and drying steps.

The laminated mat described in JP-A No. 62-66825 is a styrene-ethylene-butylene-based mat with a styrene content of 14% and an ethylene-butylene rubber phase content of 86%.
An adhesive for laminated mats is manufactured using a styrene block copolymer and without the use of tackifiers or liquid resins, but this composition does not adhere to uneven surfaces, but has good adhesion to flat surfaces. 300 g/25 mm width or less, which is a feature of the present invention.

The self-adhesive material and adhesive selection method described in JP-A No. 54-58734 involves coating an ordinary acrylic adhesive and bonding only when pressure is applied. This differs from the concept of selective adhesion due to the difference in Also, since normal acrylic adhesive is used, 20g/c
After being attached to a non-woven fabric under +fl pressure and left for 7 days at 50"C, the adhesive strength changed significantly over time.

JP-A-61-141196, JP-A-61-172397, JP-A-61-22 related to selective adhesion method
No. 1123 and Japanese Unexamined Patent Publication No. 61-233354 are completely different from the selective adhesion of the present invention, and do not serve as a solution to the problem to be solved by the present invention.

JP-A No. 5, which is a composition similar to the adhesion selective composition of the present invention.
4-56636, JP 58-501863, and JP 62-197481 are as follows (a)~
Because the composition is different in the point shown in (C), it easily and strongly adheres to the flat film, which is a feature of the present invention, with a slight pressure, but has low tackiness to surfaces with large irregularities such as nonwoven fabrics and paper. It does not result in a selective adhesive article having the property of not substantially adhering to the surface of the material, and adhering only to the extent that it can be easily peeled off by hand even if it is pressed for a long time at high temperatures.

a) In JP-A-54-56636, polyphenylene ether is present in the system.

b) In JP-A-58-501863, the styrene content of 5EBS does not fall within the range of 20 to 40%, and the type of softener (liquid resin) used is different.

C) In JP-A-62-197481, the blending ratio of 5EBS, tackifier, and softener is different from the blending ratio of the present invention.

[Means to solve the problem]

The present inventors have completed the present invention as a result of intensive research to solve the above-mentioned problems of the prior art.

That is, the present invention contains a styrene-ethylene-butylene-styrene block copolymer, a tackifier, and a liquid resin as main components, and has an adhesive property based on 100 parts by weight of the styrene-ethylene-butylene-styrene block copolymer. The content of the imparting agent is 50 to 80 parts by weight, and the content of the liquid resin is 4
0 to 70 parts by weight of an adhesion-selective composition, and an adhesion-selective article comprising this adhesion-selective composition on at least one surface of a substrate, the center average roughness of the surface being Adhesive strength to flat films such as polypropylene (PP), polyethylene terephthalate (PI!?), and polyethylene (PE) with a diameter of 0.3μ or less is 300~
For 900g/25an width, the center average roughness of the surface is 3
Adhesive strength to surfaces with large irregularities such as non-woven fabric or paper of 0 μ or more is 1 g/25 mm width or less, and the adhesive strength is 60 g/cnl after being placed on the uneven surface and left at 50°C for 7 days with a load of 20 g/cnl. The present invention provides an adhesion selective article characterized by having a width of 25 mm or less.

In addition, in this specification, the adhesive force means the adhesive force measured by the method shown in the following example, and this value is 1 g/25
If the width is less than mm, it will not stick to the adherend, or even if it sticks, it will peel off when the tape is bent in a 180° direction, or it will not be measurable with Tensilon (under 1 g may be measured depending on Tensilon accuracy, measurement conditions, and environment) (make it impossible).

The styrene-ethylene-butylene-styrene block copolymer (SEBS) used in the present invention is a copolymer consisting of two phases: a polystyrene terminal block phase and an ethylene-butylene rubber phase without double bonds. The molecular weight of the portion is 7.000 to 20,000. The molecular weight of the ethylene-butylene rubber phase is 35,000 to 50,0
00 block copolymer with a styrene content of 20 to 4
0% by weight, the content of ethylene-butylene rubber phase is 60~
80% by weight is preferably used. Particularly preferred is one in which the styrene content is 30% by weight and the ethylene-butylene rubber phase content is 70% by weight.

The tackifier used in the present invention has a softening point of 80
C2-based petroleum resin, C7-based petroleum resin, Cs/Cq-based petroleum resin, α that is ``C or more and has an average molecular weight of 400 to 2000
Examples include polyterpene resins that are polymers of -pinene, β-pinene, or dipentene, rosin resins, and hydrogenated products thereof.

The liquid resins used in the present invention include high-boiling aromatic hydrocarbon resins with a softening point of 10°C or lower and -5°C or higher and an average molecular weight of 200 to 700, polybenthene hydrogenated liquid resins, polyterpene liquid resins, and rosin liquid resins. etc.

The blending ratio of 5EBS, tackifier and liquid resin in the adhesive selectivity composition of the present invention is 50 to 80 parts by weight of the tackifier and 4 parts by weight of the liquid resin to 100 parts by weight of 5RBS.
It is 0 to 70 parts by weight. If the blending ratio of the tackifier is less than 50 parts by weight, it can be applied to a highly uneven surface and the
Adhesive strength (hereinafter referred to as
Adhesive strength under pressure at 50°C over time (abbreviated as "adhesion strength") is 60g/2
The width will be larger than 5mm. If the blending ratio of the tackifier is further reduced, the adhesive strength over time under pressure at 50°C on a highly uneven surface will reach the target value, but the adhesive strength to flat films will also decrease, making it impossible to obtain adhesive strength of 300 g/25 mm width or more. .

On the other hand, when the blending ratio of the tackifier exceeds 80 parts by weight, the tackiness increases, and as a result, the adhesive strength to a highly uneven surface exceeds 1 g/25 mm width, and the adhesive strength under pressure at 50°C over time is 60 g. /25++tm width becomes larger.

Furthermore, if the blending ratio of the liquid resin is less than 40 parts by weight with respect to 100 parts by weight of 5EBS, the melt viscosity at 180° C. exceeds 200,000 cps, making true melt coating difficult. Also, because the proportion of tackifier increases, the adhesive strength to the flat film is 900 g/25
- Exceeds the width. When the proportion of the liquid resin is further reduced, the viscosity not only increases, but also the tackiness decreases and the adhesion to the flat film surface decreases.

On the other hand, if the blending ratio of liquid resin exceeds 70 parts by weight, the fluidity will increase, so the temperature at 50°C under pressure on a highly uneven surface will increase.
If the adhesive strength changes over time is thicker than 60 g/25 mm width, it will tear on uneven surfaces such as non-woven fabrics.If it exceeds 80 parts by weight, it will completely adhere to uneven surfaces and will not be able to be peeled off.

Since the adhesion selective composition of the present invention is applied to at least one side of the substrate by hot melting at 180"C or less, in addition to 5EBS, tackifier, and liquid resin, an antioxidant is added at 1% per 5EBS. It is preferable to add up to 3% by weight.As the antioxidant, Irganox 1010 (manufactured by Ciba-Geigi), Irganox 1076 (manufactured by Ciba-Geigi), Sumilizer GM (manufactured by Sumitomo Chemical), etc. are used.

Substrates used in the adhesive selective article of the present invention include polypropylene film, polyethylene film, polypropylene/polyethylene blend (PP/PH=3
/7) Films, plastic films such as polyester films, paper, nonwoven fabrics, cloth, etc. alone or in composites can be mentioned.

The adhesion selective article of the present invention has a flat surface (center average roughness R
The adhesion strength to surfaces with large irregularities (Ra = 30μ or more) is 1g/25mm width, which is the same level as ordinary adhesive tape (300 to 900g/25mm width) (Ra = 30μ or more). It is necessary that the width is 25 mm or less. Adhesive strength to adherend surfaces with large irregularities is 1g/25mm
If it is larger than the width, attach an adhesive selective article to 20g/
After applying a load of cIiY and leaving it for 50"07 days, the adhesive strength increases, which may damage the surface of the adherend and cause adherend substances to adhere to the adhesive surface, reducing the adhesive strength and causing problems in subsequent use. comes out.

〔Example〕

EXAMPLES Hereinafter, the present invention will be explained in more detail with reference to Examples, but the present invention is not limited to these Examples.

Example 1 A copolymer with a styrene content of 30% by weight as 5EBS,
A C2-based petroleum resin was used as the tackifier, a high-boiling aromatic hydrocarbon resin was used as the liquid resin, and Irganox 1010 (pentaerythrityl-tetrakis (3-(3,5-di- t-butyl-4-hydroxyphenyl)propionate]) 5E
The mixture was mixed in an amount of 3% by weight with respect to BS and kneaded for 40 minutes using a kneader at 180°C to prepare various adhesion selective compositions shown in Tables 1 and 2.

The resulting adhesion selective composition was heated to 180° C. to form a polypropylene/polyethylene blend (PP/PE=
3/7) Coated on film, film thickness 60±5μ
An adhesive selective tape was obtained in this manner.

The obtained adhesive selective tape was tested by the following method to determine its adhesion to a two-wheel stretched polypropylene film (OPP) with a center average roughness (Ra) of 0.01μ and a nonwoven fabric with an Ra of -50μ, and to evaluate the adhesive strength of the nonwoven fabric under pressure over time. Changed adhesive strength was measured at 20° C. and 265% RH. In addition, the melt viscosity of various compositions was measured using a B-type viscometer,
The surface roughness was measured using a surface roughness meter according to JIS B 0601.

The results of examining the amount of tackifier added are shown in Table 1, and the results of examining the amount of liquid resin added are shown in Table 2.

<Adhesive Strength> As shown in FIG. 1, by using the double-sided tape 4, the adhesive selective composition coated side 2 of the adhesive selective tape 1 having a width of 25 plates is coated with a biaxially stretched polypropylene film or nonwoven fabric 3.
Gently apply adhesive selective tape 1 on top of 1kg roller 1
After crimping the stainless steel plate (SUS304) 5 by reciprocating, the loose part is 180° to the stainless steel plate 5.
Fold, stainless steel plate 5, and adhesive selective tape 1
The loose parts were sandwiched between the lower chuck 7 and the upper chuck 6, respectively, and the resistance value when pulled at a peeling speed of 300 m/min using a tensile tester within 20 seconds was measured, and this was taken as the adhesive strength.

<Adhesive strength changes over time at 50°C under pressure> By using double-sided tape, the adhesive selective composition coated side of the adhesive selective tape with a width of 25 mm was lightly applied to a nonwoven fabric, and a 1 kg roller was applied from above the adhesive selective tape. After pressure bonding to a stainless steel plate (SUS304) in one reciprocation, a load of 20 g/cJ was applied from above the adhesive selective tape and left at 50° C. for 7 days. Thereafter, the adhesive strength was measured after being left at 20° C. and 965% RH for 30 minutes or more.

Table 1 (Note) The molecular weight of City 1:5 EBS is 7,000 for the styrene portion and 35,000 for the ethylene/butylene portion.

*2: The molecular weight of the Cs-based petroleum resin is 600.

Book 3: The molecular weight of the high-boiling aromatic hydrocarbon resin is 320.

Table 2 (Note) The molecular weight of this 1:5 EBS is 7,000 for the styrene portion and 35,000 for the ethylene/butylene portion.

Book 2: The molecular weight of the Cs-based petroleum resin is 600.

*3: The molecular weight of the high-boiling aromatic hydrocarbon resin is 320.

Measured using a Hon 42 B type viscometer *5: Completely adheres to the non-woven fabric and the non-woven fabric breaks down Table 1.2
As shown, the products of the present invention Nα3, 4 and 7.8 have an adhesive strength of 300 to 900 g to flat films such as OPP.
/25+na+width, and the adhesive force to uneven surfaces such as nonwoven fabrics is 1 g/25 mm width or less, and even if a pressure of 20 g/c [50 mm] is applied to the uneven surface and left for 07 days, the adhesive force is 60 g /25- Medium or below adhesion, only enough to be easily peeled off by hand.

〔Effect of the invention〕

The adhesive-selective composition and adhesive-selective article of the present invention adheres to flat films, hardly adheres to uneven surfaces, and has little change over time, so it is suitable for articles that require high adhesive selectivity and for peeling off. It can be used for items that require adhesive tape and can be easily pasted incorrectly (for example, disposable diapers).

In addition, the selective adhesive composition and selective adhesive article of the present invention do not require protection of the surface of the composition because they do not adhere to other parts as long as they are on a highly uneven surface during storage.

[Brief explanation of the drawing]

FIG. 1 is a diagram showing a method for measuring adhesive force. 1: Adhesive selective tape 2: Adhesion selective composition application surface 3: Biaxially stretched polypropylene film or nonwoven fabric 4; Double-sided tape 5 Ni stainless steel plate (SUS304) 6: Upper chuck 7: Lower chuck Applicant's agent Kaoru Furutani

Claims (1)

[Claims] 1. Contains a styrene-ethylene-butylene-styrene block copolymer, a tackifier, and a liquid resin as main components, based on 100 parts by weight of the styrene-ethylene-butylene-styrene block copolymer. An adhesion selective composition characterized in that the content of the tackifier is 50 to 80 parts by weight, and the content of the liquid resin is 40 to 70 parts by weight. 2. The adhesion selective composition according to claim 1, wherein the styrene content of the styrene-ethylene-butylene-styrene block copolymer is 20 to 40% by weight. 3. The tackifier has a softening point of 80°C or higher and an average molecular weight of 40
0 to 2000 C_5 petroleum resin, C_9 petroleum resin,
C_5/C_9 petroleum resin, polyterpene resin which is a polymer of α-pinene or β-pinene or dipentene,
The adhesion selective composition according to claim 1, which is a resin selected from the group consisting of rosin resins and hydrogenated products thereof. 4. The liquid resin is a high-boiling aromatic hydrocarbon resin with a softening point of 10°C or lower and -5°C or higher and an average molecular weight of 200 to 700;
The adhesion selective composition according to claim 1, which is a resin selected from the group consisting of a polypentene hydrogenated liquid resin, a polyterpene liquid resin, and a rosin liquid resin. 5. An adhesive-selective article comprising the adhesive-selective composition according to claim 1 on at least one surface of a substrate, which has adhesive strength to a flat film having a center average roughness of 0.3 μ or less. 300 to 900g/25mm width, the adhesive strength to a highly uneven surface with a center average roughness of 30μ or more is 1g/25mm width or less, and a load of 20g/cm^2 is placed on this highly uneven surface. An adhesion selective article characterized in that the adhesive force after being applied and left at 50°C for 7 days is 60 g/25 mm width or less.