JPS58215474A - Urethane adhesive composition - Google Patents

Abstract

PURPOSE:To provide the titled compsn. well suited to adhesives for non-rigid polyvinyl chloride tapes, by incorporating a butadiene polymer, a compd. reactive with isocyanates, polyisocyanates, petroleum resin, and plasticizer. CONSTITUTION:A butadiene polymer (A) having two or more hydroxyl groups at the terminals (MW; 500-5,000), a compd. (B) having an aromatic ring and two or more functional groups reactive with isocyanates, in an amt. corresponding to the active hydrogen equivalent 0.5-3 times as much as that of component A (MW; 150-500), a polyisocyanate (C) in an amt. corresponding to the isocyanate equivalent 0.6-1.2 times as much as the total active hydrogen equivalents of components A and B, 10-100pts.wt., based on 100pts.wt. total amt. of components A, B and C, petroleum resin (D) unreactive with isocyanates (softening point; 50-150 deg.C), and 5-40wt%, based on the total amt. of compsn., plasticizer (E) are blended together.

Description

DETAILED DESCRIPTION OF THE INVENTION This invention relates to an adhesive composition that is used in the adhesive or adhesion areas of zero-release IJIii pressure-sensitive adhesive tapes, sheets, cupels, etc., and is particularly suitable for use as a soft vinyl chloride bonding agent.

Conventionally, in order to produce light-sensitive adhesive tapes, etc., a solution of an adhesive in a solvent Kfti was applied to a base tape, etc., and the solvent was evaporated and dried to form an adhesive layer. This method of using a solvent deteriorates the working environment because air is mixed into the final agent, complicates the process by requiring drying and solvent recovery steps, and is difficult to recover the solvent in a high yield at low cost. In order to overcome these drawbacks, solvent-free adhesives that do not use solvents have recently been proposed.

For example, a composition consisting of a diene polymer having two or more functional groups in one molecule that can react with incyanate groups, a polyisocyanate compound having two or more isocyanate groups in the molecule, and a tackifying resin is used as a tape base. It is known that a pressure-sensitive adhesive is formed by applying the composition onto a material and reacting the functional groups in the composition by heating or the like, and as the tackifier resin, as shown in Tokuho No. 1153-9778 Publication 411K, In order to uniformly dissolve the resin components in the adhesive layer, alkylphenols CH, OH, -0■, -C
Those having polar groups such as OOH groups were used.

However, when using the button self-adhesive resin described in item 11, the polar group in the molecule reacts with the inreanate group.
There is an economic disadvantage in that an expensive polyisocyanate compound must be used in excess, and when a rosin resin containing a -C00H group is used, the -C00II group reacts with the incyanate group to generate carbon dioxide gas bubbles. There are drawbacks such as generation and roughening of the adhesive 111 surface, and there are also disadvantages such as alkyl phenol resin, terpene phenol resin, etc.
When enol AtJ1 fat is used, the phenol in the molecule combines with inreanate to form a phenol-type blocked isocyanate, and then incyanate is gradually regenerated from this, causing changes in the structure and physical properties of the adhesive. It has the disadvantage that the adhesive@O performance deteriorates over time.

On the other hand, if a plasticizer is used in the adhesive layer of a soft vinyl chloride tape, the plasticizer in the tape will be viscous.
VC should contain a plasticizer in the adhesive composition forming the adhesive layer in order to gradually degrade the physical properties of the adhesive layer and prevent the plasticizer from migrating to the adhesive layer. However, if a plasticizer is simply added to a Frethane pressure-sensitive adhesive composition containing a getadiene polymer, the cohesive force of the pressure-sensitive adhesive decreases, high tackiness or adhesive strength is lost, and tackiness is increased. It is difficult to obtain a plasticizer-containing pressure-sensitive adhesive composition that can be put to practical use, as there is a strong tendency for the compatibility of components such as adhesives to decrease, making it difficult to maintain stable high adhesion. I understand.

In view of the current state of pressure-sensitive adhesive compositions as described above, the present invention eliminates the need for the polyisocyanate compound to be consumed excessively by the tackifying resin and eliminates the disadvantages of using the rosin-based or phenol-based tackifying resin. The purpose of this invention is to provide a plasticizer-containing adhesive composition that can be used as a solvent-free adhesive composition and can be particularly suitably used for soft vinyl chloride tapes. Butadiene-based poly7-me with a molecule of 1 soo to 50005-, which has two or more hydroxyl groups at the terminal VC, and a compound B with a molecular density of 150 to SOO, which has an aromatic ring in the molecule and has two functional groups that are reactive with isocyanate. Aromatic or aromatic-aliphatic petroleum resin which has no reactivity with isocyanate and has a softening point of 50-150'C, and which has two or more incyanate groups in the molecule. In a composition containing reagent E, the hq water volume of compound B in the composition is α5 to 3 times that of active hydrogen of butadiene-based polymer A, and inocyanate of polyisocyanate C. The number of equivalents is 6 to 12 times the total active hydrogen of the getadiene polymer and compound B, and the equivalent number of the oil tree fMD is 100 parts by weight of the getadiene polymer A, compound B, and polyisoleanate c. against 1
0 to 10011111 parts, and the amount of plasticizer Ef) is 5 to 401i1% of the composition.

In order to produce a phrethane resin by reacting the pucdiene-based polymer used in the present invention with inreane-1, it is necessary to have two or more hydroxyl groups at the molecular end, and the molecular weight is low. If the molecular weight is too high, the adhesive layer formed by using the composition of the present invention will not be able to exhibit the elasticity required as an adhesive, and if the molecular weight is too high, the viscosity of the composition will become too high at room temperature, making it unusable. H3O is defined as 0-5000, more preferably 1000-3000.

The butadiene-based polymer A can be produced by introducing a hydroxyl group at the end of a getadiene polymer, and is easily available as a commercial product. In the present invention, it is preferable to use a polymer in which about 60% or more of the butadiene units constituting the polymer chain are L4-bonded, giving the resulting adhesive layer a high degree of elasticity and adhesion. This is preferable from the viewpoint of improving the performance of the layer. Further, as the polymer A, it is also possible to use a polymer containing a small amount of a copolymer component such as styrene or acrylonitrile in the polymer chain.

Next, in the present invention, a molecule 11 having an aromatic ring and two functional groups reactive with incyanate is used.
50-600 preferably 200-300 chemical compound 44&+B
Compound B is reacted with polyisocyanate C together with butadiene-based polymer A, and is incorporated into the resulting polyflexine chain, and due to the structure having an aromatic ring in the molecule, the adhesiveness provided as a result of the reaction - Aromatic petroleum resin I) which is added as a 4-adhesive agent to further improve adhesive strength by increasing the cohesive force of
This has the effect of improving the compatibility with the 1# fat component in the viscous INH, and allowing the adhesive layer to stably exhibit its excellent adhesive strength.

In order to fully exhibit the above-mentioned effects in the present invention, the compound Bθ is used as a compound having an active hydrogen equivalent of a5 to 3 times the bulk water equivalent of the getadiene polymer. be done.

Further, the functional group t of the compound B is not particularly limited as long as it has reactivity with incyanate, but it is particularly preferable that the functional group is an aliphatic hydroxyl group or an amino group. Suitable examples of the compound B include N,N(di-2hydroxypropyl)aniline, bisphenol A
Adding propylene oxide to the phenol end of CH
, -CH-OH, propylene oxide adduct or ethylene oxide adduct of biphenylCH3-4,4' diol, propylene oxide adduct or ethylene oxide adduct of 1,5+m clean diol, Examples include 4.4'-diaminodiphenylmethane.

In addition, as the polyisocyanate C having two or more inocyanate groups in the molecule used in the present invention, polyisocyanates such as tolylene diisocyanate and diphenylmethane diisocyanate, which have been conventionally used in the production of boriclecne, and polyol compounds can be used. Polymers having two or more incyanate groups tH in the molecule formed by reacting polyisocyanate 9-ester are mentioned. The amount of polyisoleanate C to be used is such that the adhesive produced from the zero-start composition has excellent physical properties such as adhesiveness, and is also economically advantageous. The isoleate ratio-equivalent number of t groups contained in polyisocyanate C is α6~L due to the total active water group equivalence between the butadiene-based polymer A and &*B! It is preferably 7 to L' 0 times to t'i.

Further, in the present invention, an aromatic or aromatic-aliphatic copolymerized petroleum resin resin having a softening point of 50 to 150°C and which is reactive with incyanate is used. It is used as a tackifier, and unlike other tackifiers on tilbenzenol resins, such as lurosin and tilbenzenol resins, which are conventionally used, it is expensive. Extra VCil polyisocyanate! In addition, there is no problem of generation of gas in the adhesive layer 10 as a by-product due to the reaction with the incyanate, or deterioration of physical properties such as adhesiveness over time due to the incyanate regeneration phenomenon. be. Moreover, the resin resin is the butadiene-based polymer A.
1 Compatibility with Compound B and with polyurethane produced by the reaction of these compounds with polyisocyanate are good, so it is similar to the case when a non-functional aliphatic tackifier is used. It does not cause a decrease in adhesion due to phase separation. The amount of the petroleum resin used is in the range of 10 to 100 parts by weight per 100 parts by weight of the total amount of the butadiene-based polymer A1 compound B and polyisocyanate C in order to exhibit appropriate tackifying properties.

However, this petroleum resin can be obtained by polymerizing the C11 fraction or by copolymerizing the #''i C@ fraction with the C4 or CSS fraction, and among these,
Those having a softening point of 60 to 150°C are preferably used. or,
It is preferable that the molecule M#'i@SOO~1500. It is easily available as a commercial product, and suitable examples of the 1νIK used in the present invention include Vetrogin, FTR,
Cook Ace (all product names manufactured by SanHfi Oil Chemical Co., Ltd.)
, Hi-Resin (trade name, manufactured by Toho Sekiyu Co., Ltd.) is an example.

In addition, in the present invention, 5 to 40% by weight of the plasticizer E of the composition is added, and the plasticizer may be a commonly used #J such as 7-talate ester or adipine ester.
11 agents may be used, and soft vinyl chloride! Cash register I-^
L < $4 Shizu & tj, U used as adhesive for tape
The use of iSm agents similar to those used in soft thermoplastic vinyl sufficiently prevents the transfer of plasticizer from the sheet or tape substrate to the adhesive and maintains excellent adhesion properties over long periods of time. It is preferable in that it does.

As stated in the IJI adhesive composition from scratch, getadiene polymer A1 compound B1 polyisocyanate C1 stone ^1
1 resin and plasticizer E in predetermined proportions, but it is also possible to contain a reaction catalyst, anti-aging agent, filler, and other additives as required.

K used in the adhesive composition of the present invention can be applied to a base material such as a sheet or tape, and heated etc. to react the hydroxyl groups and incyanate groups contained in the composition. The material loses its initial fluidity and becomes a sticky layer with excellent adhesion. Therefore, the composition of the present invention can be suitably used as a solvent-free adhesive composition that does not require the use of a solvent.

Since the pressure-sensitive adhesive composition of the present invention has the above-mentioned structure, the pressure-sensitive adhesive produced from the composition has excellent adhesion, has good compatibility of each component, and prevents bleeding of tackifiers, etc. It is possible to maintain a stable VcM for a long period of time with its excellent adhesion without causing any tackifier, and it is highly economical as it does not consume excess polyisocyanate component unlike conventional tackifiers when forming the adhesive layer. At the same time, it does not cause the generation of bubbles or adhesive fading over time due to the reaction between the polyisocyanate component and conventional tackifiers such as rosin and terpene phenol, and is a solvent-free type. It shows excellent performance when used as an adhesive composition.

Furthermore, Composition 1 of the present invention is particularly suitable for use in soft vinyl chloride because it contains an iJ warming agent.The present invention will be explained below by Suiseoka.

In addition, the term "part" below means the irises part.

Example 1 Polycitadiene small sebolimer with terminal hydroxyl groups having an average molecular weight of 2800 (average hydroxyl groups 'L3 per molecule) 10
0 parts, 17.6 parts of N,N(di-2-hydroxyglobil)aniline (active hydrogen equivalent & double the active water volume of polybutadiene), aromatic petroleum resin (trade name Vetrozin, Mitsui 25 parts of diphenylmethane diisocyanate (NC 010 ,
Add 1 part to Diptyl pot silacrate and mix to make an adhesive, apply this to a 160p thick soft vinyl chloride sheet h with a roll coater to a thickness of 30μ, and heat at 110°C for 2 minutes. After curing, an adhesive tape was obtained.

When the obtained tape was used as a sample and tested for the following items, the results shown in Table 1 were obtained.

SP adhesive strength: A 20m medium sample was pasted on a stainless steel plate, pressed with a two-speed rubber roll back and forth once, and left to stand for 15 minutes, then peeled 180° at a rate of 300cm/- at 20°C to determine the peel strength. It was measured.

Ball tack: Measured based on J, DOW decision.

Measurement temperature: 20°C, unit: 1/32 inch.

Gel fraction: 48% adhesive in tetrahydrofuran at 40℃
After soaking for a period of time, the eluted matter was removed, and the undissolved matter was expressed as a percentage.

Example 2 Aromatic petroleum resin (vetrozine) 71 in Example 1
Aromatic-aliphatic copolymer petroleum resin (product name F
An adhesive tape was produced in the same manner as in Example 1, except that 71 parts of TR, manufactured by Mitsui Oil & Petrochemical Co., Ltd. (100°C) were used.
When we conducted a test Wk on this, we obtained the results shown in Table 1.

Example 3 Example 1 33 parts of a compound obtained by adding globylene oxide to the 7-enol tree 1611i of bisphenol A in place of N,N (di-2-hydroxypropyl)aniline in fCir (2 parts per active hydrogen of polybutadiene) 6
The same tar as in Example 1 was used except that 6% water bulk equivalent) was used.
An adhesive tape was manufactured and tested.

Comparative Examples 1 to 3 Implementation 11AJ IKh Replacement of aromatic petroleum resin (Vetrozin) 6c No II functional aliphatic resin (trade name Kokoretsu, Esso Co., Ltd. Ws Softening a 1 G G ℃)
In the same manner as in Example 1 (comparison H1), 71 parts of rosin resin (trade name Ester Gum HP, manufactured by Arayo Kagaku Co., Ltd., softening point 90'C) was used. (Comparative Example 2), the same terpene phenol resin (
Product name: Ys polyster, manufactured by Yasushi Oil Co., Ltd., softening point 100'
C) When 71 parts were used (Comparative Example 3), an adhesive tape was manufactured and tested, and the results were as shown in Table 1.

In Comparative Example 2, foaming occurred during curing of the adhesive layer, and the adhesive layer did not solidify and became stringy. Comparative example 3
Similarly to Comparative Example 2, the adhesive did not harden and became stringy.

Comparative Example 4 7 tl of terpene phenol resin (same as Comparative Example 3) was used instead of the aromatic petroleum resin (vetrozin) of Example 1, and 35 parts of incyanate (N0010H in the composition) was used instead of 25 parts of diphenylmethane diisocyanate. Adhesive tapes were produced in the same manner as in Example 1, except that the equivalent ratio L12) was used, and tests were conducted to obtain the results shown in 1st jEK.

Comparative Example 5 17- Comparative Example 40 A thickening agent was prepared, and curing was performed at 110°C for 5 minutes instead of 110°C and 2 minutes of darkness.

Comparative Example 6 In place of N, N (di-2-hydroxypropyl) aniline in Example 1, Kl, 7.5 parts of 4-gutanediol (2 times the active hydrogen volume per lti water volume of polybutadiene) was used except that Similarly to Example 1, 90=18-

Claims (1)

[Claims] L Molecular weight 50 having two or more hydroxyl groups at the molecular terminal VC
0 to 5,000 butadiene-based polymer A has an aromatic ring in one molecule and contains two functional groups that are reactive with incyanate.
Compound B1 having a molecular weight of 150 to 500 VC within the molecule
A polyisocyanate containing two or more incyanate groups, which is reactive with C1 isocyanate and has a softening point of 50 to
A composition containing an aromatic or aromatic-aliphatic copolymerized petroleum resin and a plasticizer Et at 150°C,
The number of active hydrogen equivalents of compound B in the composition is 15 to 3 times the number of active hydrogen equivalents of butadiene-based polymer A, and the number of incyanate equivalents of polyisocyanate C is the total number of active hydrogen equivalents of getadiene-based polymer A and compound B. The amount of petroleum resin is 10 to 100 parts by weight per 100 parts of valve composition of sitadiene-based polymer A1 and polyisocyanate C, and the amount of petroleum resin is 10 to 100 parts by weight. 1. A flexible pressure-sensitive adhesive composition having a weight of 5 to 40 and a weight of 96. 2. The flexible pressure-sensitive adhesive composition according to item 1, wherein the butadiene-based polymer A is a polymer @tm in which about 6096 or more of the butadiene W positions are L4-bonded. The phletane adhesive composition according to item 1 or item 2, wherein the v81 resistance of compound B is either an aliphatic hydroxyl group or an amino group.