JPS59230076A - Urethane pressure-sensitive adhesive composition and its use - Google Patents

Abstract

PURPOSE:The titled composition useful for non-rigid vinyl chloride tape, providing improved pressure-sensitive properties and tape characteristics stably, containing a specific polyol compound previously processed into a high polymer compound and a polyisocyanate compound in a specific ratio. CONSTITUTION:(A) A polyol compound (having 5,000-30,000mol.wt., and 2-2.4 functional groups) obtained by reacting (i) a polyol component containing >=15wt% polybutadiene compound (preferably having 1,000-5,000 number-average molecular weight, and 2.2-2.4 functional groups) having >=60wt% butadiene unit of 1,4-bond, and terminal hydroxyl groups with (ii) a polyisocyanate in an equivalent ratio (NCO/OH) of isocyanate group in the component ii to hydroxyl group in the component i of 0.2-0.65 is blended with (B) a polyisocyanate compound in an equivalent ratio of isocyanate group in the component B to hydroxyl group in the component A of 0.6-1, to give the desired composition.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention provides a urethane adhesive composition that is used for pressure-sensitive adhesive tapes, adhesive tapes, labels, etc., and is particularly suitable as an adhesive for soft vinyl chloride tapes. and how to use it.

Conventionally, to manufacture pressure-sensitive adhesive tapes, etc., a solution of an adhesive dissolved in a solvent was applied to a tape base material, etc., and the solvent was evaporated and dried to form an adhesive layer. However, the method of using a solvent has the problem of deteriorating the working environment because the solvent scatters. In addition, there are drawbacks such as the complexity of the equipment process for drying and solvent recovery, and the difficulty in efficiently recovering the solvent, so many solvent-free adhesives that do not use solvents have been developed. .

For example, it is known that a solvent-free adhesive can be obtained by reacting a prepolymer having icyanate groups at both ends with a polyol having hydroxyl groups at both ends. The physical properties of the tape are affected by the humidity during the formation of the adhesive layer, making it difficult to obtain stable performance. Furthermore, the physical properties of the tape obtained are not fully satisfactory, and this is thought to be due to the fact that the iso7anate group reacts with moisture in the air and the polymer chain length is not sufficiently extended.

In JP-A-56-82864, the unevenness of the adhesive layer (
In order to prevent repellency, the active hydrogen group-containing compound component, which is made of butadiene homopolymer having hydroxyl groups at both ends, is reacted with organic shitsuquanate to polymerize it, and has at least one active hydrogen at the end. and a composition containing a polyicanate component.

However, even in this composition, the adhesive performance and tape physical properties are not satisfactory.

This is because, according to a general rule confirmed by the inventor, the one- and two-bonded butadiene units constituting the butadiene homopolymer of the composition proposed in the above-mentioned publication tend to increase the elasticity of the polymer. The number of functional hydroxyl groups in the butadiene homopolymer tends to decrease by 2 to 9, and it is considered that the blending ratio of the butadiene homopolymer, polyiso/anate, etc. is not within the optimal range. This product eliminates the drawbacks and is mainly composed of a pre-polymerized polyol compound and a polyic anate compound, which allows the polymer chain length of the polyol compound to be sufficiently extended, resulting in good adhesive performance and stable tape physical properties. The purpose of the present invention is to provide a V-tan type adhesive composition that can be obtained according to the method of the present invention and a method for using the same.

The phrethane pressure-sensitive adhesive composition of the present invention basically comprises a polyol compound (C) and a polyiso7anate compound (D), which have been polymerized in advance. and,
The polyol compound (C) is a polyol component (4) containing 15 weight or more of a polybutadiene compound (A) having a hydroxyl group at the end and a polyiso7anate compound (B).
are mixed and reacted.

A polybutadiene compound (A) having a hydroxyl group at the terminal has 60 1,4-bonded butadiene units out of 7.
It accounts for more than % by weight and has a hydroxyl group at the end. Moreover, the compound (A) is partially branched from the double bond of the butadiene unit, and as a result, the functional group (hydroxyl group) is 2 on average.
．． It has 0 to 2.5 pieces. Note that the average number of functional groups is preferably 2.2 to 2.4. This is because the final polymer has a network structure.

The number average molecular weight of the compound ranges from 500 to 5,000, preferably from 1,000 to 3,000. In addition to the 1,4-bonded butadiene unit, the compound (4) may contain IC1,2-bonded butadiene units and other units as constituent units.

1.2-It is expected that the branched vinyl group of the bonded butadiene unit will physically engage with the molecule on the side to be adhered.

It may also be a butadiene homopolymer in which l,4-bonded butadiene units account for 100% by weight.

As the 1.4-linked butadiene units approach 100% by weight of the compound (in the box), the resulting polymer as a whole tends to become more flexible and tackier.
, 1.2- When the proportion of bonded butadiene units increases, and 1.4- When the bonded butadiene units approach 60% by weight, the resulting polymer as a whole becomes highly elastic and rigid, making it difficult to use adhesive tape. When peeled off, no adhesive tends to remain on the adhered side, but the adhesiveness tends to decrease slightly.

In addition, polybutadiene compounds composed only of 1.2-bonded butadiene units have a number of terminal hydroxyl groups less than 2 and an average of 1.5 to 1.7, and have a network structure. K used as a polymer was inappropriate.

The polyol component diagram may include compounds having hydroxyl groups other than polybutadiene compounds having hydroxyl groups at the ends.

Among the compounds constituting the polyol component diagram, in addition to the polybutadiene compound (A) having a hydroxyl group at the end, there are compounds having an aromatic ring and two hydroxyl groups.

The compound (A) having an aromatic ring and two hydroxyl groups is inserted into the polyiso/anate compound (B) when the polybutadiene compound and the polyicanate compound (B) react to form a polymer. It has the effect of extending the chain length of the polymer by reacting with the iso7anate group of . Furthermore,
The compound (A) having an aromatic ring and two hydroxyl groups imparts rigidity to the resulting polymer, has 1,4-bonded butadiene units accounting for 60 or more by weight, and has a hydroxyl group at the end. It also has the effect of supplementing the flexibility of the polybutadiene compound (A) and bringing the elasticity of the resulting polymer into a range preferable for use as an adhesive.

Examples of such compound (A) include the following. That is, bisphenol AK with some additions of ethylene glycol or propylene glycol; (R is ethylene glycol or propylene glycol,
m, n are integers from 2 to 1O) or N, N-di-2-oki7probylaniline; O
H3 ■ CH2-OH-OH Black OH3, hydroquinone di(β-hydroxyethyl) ether, etc.

Polyol component (A) contains a polybutadiene compound (A5 and a compound having an aromatic ring and two hydroxyl groups,
The polyol (A) is preferably one that is liquid at 80°C or lower, and polyols such as ethylene glycol, propylene glycol, diethylene glycol, Molecular diols, glycerin, polyhydric alcohols such as pentaerythritol, etc. are expected to act as chain extenders. In addition, polyether diols such as polyoxy-7 ethylene glycol, polyether triols such as polyoxy/propylene triol, or these polyols have intramolecular IC trimethylolpropane,
Polyester polyols such as polyether polyols co-condensed with pentaerythritol, glycerin, etc., condensates of low molecular weight glycols such as propylene glycol and organic dibasic acids such as phthalic acid, ring-opening polymers of ξ-caglolactam, 1, 2 butadiene bond with a hydroxyl group at the end is 90% by weight or more and the molecular weight is 1.000~s
, o o o polybutadiene, butadiene and styrene copolymers, butadiene and acrylonitrile copolymers, and other liquid rubbers are mentioned as the polyol (A) to be mixed and used in the polyol component (A).

In the present invention, the polyiso7anate compound CB) is an aliphatic polyicanate such as propylene diisonoanate, hexamethylene diisonoanate, tolylene diisocyanate, diphenylmethane diisonoanate, pysyl diinphanate, naphthylene diiso/aky), 4,4'-methylenebis(phenyliso7
Aromatic polyisocyanates such as 1,3-dimethylbenzene, 1
-methyl-2,4-diiso7anate/chlorohexane,
Examples include alicyclic polyiso7anates such as 4.4'methylene-bis(cyclohexyliso7anate), ω,ω'-diiso/ane)-1,3-dimethyl/chlorohexane.

Further, as the polyiso/anate compound (B), a prepolymer having an iso/anate group at the end, which is obtained by reacting the polyol listed above for the polyol component (A) with twice the chemical equivalent of diisocyanate, can be used. It is also possible to use a mixture of the above-mentioned low-molecular-weight polyinnoanates.

The above-mentioned prepolymer having an acidic anate group at the end is a polyol compound (C) obtained by reacting a low-molecular polyisocyanate, a polyol component and a polyin/anate compound CB), and a pressure-sensitive adhesive finally obtained. There is an advantage that the polymer chain length and network size of the composition can be easily designed.

The polyol compound (C) of the present invention is a polyol component)
and polyiso7anate compound (B). The polyol compound (C) may be the above-mentioned polybutadiene compound (A) having a hydroxyl group at the end alone, or if necessary, an aromatic ring and two hydroxyl groups, and further a low-molecular polyiso7ane7 or an isocyanate group at the end. The prepolymer polyic anate compound (B) is mixed and heated and stirred without a catalyst or in the presence of a small amount of catalyst. The reaction time is 30 minutes to 2 hours, and the heating is in the range of 60 to 160°C. The terminal hydroxyl group of the polyol component (A) and the terminal iso7anate group of the polyisocyanate compound (B) are reacted to form urethane. A polyol compound (C) is formed by forming bonds and becoming a polymer. The catalyst can be diptyltin crate, which is conventionally used for urethane reactions, and is 0.0001 to 1%, especially 0.0001 to 1%, based on the total weight of the polyol component (A) and polyiso7anate compound (B).
It is preferable to use it in the range of 001 to 0.1-.

Polyol component (A) and polyiso77ate compound (B
) is the equivalent ratio (
They are mixed and reacted so that NGOloI() is 13.2 to 0.65.

When the equivalence ratio (N G Olo H) is less than 0.2,
The amount of reaction between hydroxyl groups and incyanate groups is insufficient, and the chain length of the resulting polymer is not sufficiently extended.

In addition, if the equivalent ratio (NGOloR) exceeds 0.65, polymerization will proceed excessively, and crosslinking will also proceed, resulting in increased viscosity and a lack of hydroxyl groups, making it difficult to proceed with subsequent mixing, coating, and reactions. It becomes difficult.

In addition, when reacting the polyol component (A) and the polyiso7anate compound (B), the humidity should be controlled to prevent the iso7anate group from reacting with moisture in the air to form a urea bond. It is preferable to carry out the reaction in a cool atmosphere.

The obtained polyol compound (C) has a number average molecular weight of 5,
000 to 30,000, and the average number of functional groups is 2 to 2.4.

Further, when obtaining the polyol compound (C), in addition to the polyol component (A) and the polyiso7anate compound (B), an anti-aging agent, a softener, a filler, a solvent, or a tackifier as described below is added in advance. May be added. In particular, it is generally necessary to heat the tackifier in order to dissolve it, but it is preferable to add it before the reaction because the polyol compound (C) K tackifier will dissolve with good compatibility after the reaction is completed.

The adhesive composition of the present invention contains the above-described polyol compound (C) and polyincanate compound (D) as main components, and the equivalent ratio of the in7anate group of the compound (D) to the hydroxyl group of the compound (C). (NG 010H) is 0.6
It is tricked to be ~1.

As the polyincanate compound (D), the same one as the polyin/anate compound (B) described above can be used, and the same compound (D) and compound (B) can also be used. Further, as mentioned above, a prepolymer having an iso71ate group at the end is more preferable than a low molecular weight polyisocyanate.

The polyicanate compound (D) is mixed with the polyol compound (C) and heated without a catalyst or in the presence of a small amount of catalyst, so that the terminal hydroxyl group of the polyol compound (C) and the polyiso7anate compound The terminal inquanate group of (D) reacts to form a frethane bond, and polymerization further progresses, resulting in a frethane adhesive having a crosslinked structure and a network structure.

In such a reaction, the polyol compound (C) is first polymerized to have a number average molecular weight s, ooo ~ 30,000 and an average number of functional groups 2 to 2.4, so that the individual networks of the network structure are large and It spreads three-dimensionally and crosslinks, resulting in a fine crosslinked structure with increased adhesive strength and improved adhesive properties.

The above-mentioned urethane pressure-sensitive adhesive appropriately contains an aromatic or aromatic-aliphatic copolymer petroleum resin (E) that does not have reactivity with the inquanate group as a tackifier. As tackifiers, conventionally used rosins, terpene phenolic resins, and others react with the isocyanate groups, consuming an excess of expensive in/anate compounds, and the isocyanates combined with such conventional tackifiers are later removed. Regenerate to reduce adhesive properties over time.

On the other hand, aromatic or aromatic-aliphatic copolymerized petroleum resins (E) often react with iso7anate groups and do not cause the above-mentioned drawbacks, and can also be used as polyol compounds (C). It has good compatibility with the polyurethane produced from the polyicanate compound (D) and does not cause a decrease in adhesiveness due to phase separation. The petroleum resin @
) is preferably used in an amount of 10 to 120 parts by weight based on the total amount of the polyol compound (C) and polyiso7anate compound (D), ioo parts by weight, in order to exhibit appropriate tackifying properties.

However, this petroleum resin (E) can be obtained, for example, by polymerizing a C0 fraction or copolymerizing a C0 fraction with a C4 or C6 fraction, of which the softening point is 50- 150'C molecule ft5o.

~1500 is preferably used. The petroleum resin (E
) are easily available as commercial products, such as Hetrozin, FTR, Tac Ace (all trade names manufactured by Mitsui Petrochemical Co., Ltd.), and Hi-Resin (trade name manufactured by Toho Petrochemical Co., Ltd.).
f) etc. Furthermore, a plasticizer may be added as a softener to the urethane pressure-sensitive adhesive composition of the present invention. Dibutyl 7-talate, dioctyl phthalate, etc. are used as plastic WJ, but when added to the urethane-based adhesive WJ composition, the adhesive is plasticized, lowered in viscosity, and increased in coatability.
Can maintain adhesive strength at low temperatures.

In addition, the waxy adhesive composition of the present invention contains nooid o.
jP/N, anti-aging agents such as 2,6-di-tert-butyl-p-cresol, ultraviolet absorbers such as 2,4-dihydro-7penzophenone, 2-(2'-hydroxy-51-methylphenyl)benzotriazole It may also contain agents, pigments, fillers, catalysts or solvents.

The solvent here is a polymerized polyol compound (C) and a polyin 7-anate compound (necessary for improving the coating properties of the V-Tan adhesive composition containing DJ as the main component by reducing the viscosity of the adhesive composition). Rather than using conventional solvent-based adhesives at a ratio of 400 to 500 parts by weight per 100 parts by weight of adhesive solids, it is used at a ratio of 10 to 50 parts by weight at most. , and even if the solvent needs to be recovered afterwards, it can be carried out easily.

Adhesive film using the urethane adhesive composition of the present invention,
K, which manufactures foot or tape, mainly contains a polyol compound (C) and a polyin 7-anate compound (D) on the surface of a base material such as a polyester film, soft vinyl chloride film, nonwoven fabric, synthetic resin or rubber foam, or Japanese paper. The urethane pressure-sensitive adhesive composition as a component is applied and heated to cause compound (C) and compound (D) to react. After that, it is rolled up together with the base material or cut to form a product. The above heating can be performed by simply heating air to 80 to 180°C and bringing it into contact.

At this time, humidification or dehumidification may be performed if necessary.

As explained above, in the present invention, the inquanate compound, which naturally reacts sensitively with moisture in the air, is polymerized to the extent possible in advance and incorporated into the polyol compound (C), and the remaining inquanate compound ( Since the main component is a polyol compound (C) which is a polymer of D), contact between moisture and icanate on the surface of the product base material is minimized, so stable adhesive properties can be obtained. In addition, it is possible to prevent the growth of polycrethane from being stopped due to moisture, and high-performance adhesive properties can be obtained.

In the present invention, in the polyol component (A), 60 weight -
Since the polybutadiene compound article with a hydroxyl group at the end accounts for more than 15% by weight, the final poly-9-urethane produced has an appropriate crosslinked structure and network structure, and the degree of elasticity of the polymer is also tacky. Since it is a suitable agent, the resulting adhesive properties are good.

Furthermore, in the present invention, a polyiso7anate compound (
Polyol compound (C) that has been polymerized in advance together with B)
and polyiso7anate compound (D) as the main components, the pot life in coating is extended and the time required for reaction on the substrate is shortened, making coating easier and making it easier to manufacture products. The speed increases dramatically.

Furthermore, since the present invention uses no solvent or a very small amount of solvent, manufacturing is facilitated and the working environment is improved.

Hereinafter, some examples will be shown to confirm the effects of the present invention. In the Examples, parts indicate parts by weight, and % by weight. In addition, each test item shown in the following examples was measured by the following method.

SP adhesive strength: A sample with a width of 20 m is pasted on a stainless steel plate, and a 2 kg rubber roll is pressed back and forth once, and immediately after leaving it for 15 minutes, it is applied at a speed of 300 txm/m at 20°C.
The film was peeled off at 80° and the peel strength was measured.

Ball tack; r, measured based on the Dow method.

Measurement temperature 20℃, unit 1/32 inch Nchi.

Holding force: Paste the sample in an area of 1 inch x 1 inch on a stainless steel plate, press the rubber roll in step 2 back and forth once, leave it at 40°C for 15 minutes, and then apply a load of 1 cI kg to the lower end of the sample. The stainless steel plate was held vertically and the length of displacement was measured after 24 hours.

Low-temperature development force: After leaving the rolled sample tape in a freezer at -10°C for 24 hours or more, the development force was measured when it was unfolded at a constant speed of 60 m/-.〇<Example 1> An average of 21 .A polybutadiene compound with 3 hydroxyl groups and 80 1,4-bonded butadiene units (number average molecular weight 2800, trade name PBd-R45H)
T, manufactured by Izumoto Petrochemical Co., Ltd.) 100 parts, bisphenol A
Diol with about 10 molecules of ethylene glycol added to both ends of polypropylene glycol (molecular weight 654, trade name BA-10, 27.2 parts per Nippon Nyukazai Co., Ltd.), polypropylene glycol with trilene glycol condensed at both ends. 75.9 parts of a rianate compound (number average molecular weight 1656, trade name Takenate L1128, manufactured by Narita Pharmaceutical Co., Ltd.) were mixed,
Add to a 500oc separable flask and stir.
The mixture was heated to 20'C and reacted for 2 hours to obtain a polyol compound (hereinafter referred to as POH-1). This POH-1
was a viscous liquid at room temperature, and there was no absorption of in7anate group in the infrared absorption spectrum.

<Example 2> In place of the diol (BA-10) in Example 1, a diol in which approximately three molecules of propylene glycol were added to both ends of bisphenol A (molecule n38o).

The experiment was carried out in the same manner as in Example 1, except that 15.8 parts (trade name: BAP-3, manufactured by Nippon Nyukazai Co., Ltd.) was added. The obtained polyol compound is designated as POH-2.

<Example 3> Geo-# (BA-10) K replacement terminal of Example 1.

An experiment was conducted in the same manner as in Example 1 except that 4.9 parts of 6-hexanediol was added. The obtained polyol compound is designated as Pot(-3).

<Example 4> A polybutadiene compound having an average of 1.7 hydroxyl groups at the terminal and 90 parts or more of l,2-bonded butadiene units (number average molecular weight 1400°, trade name N15so)
50 parts of PBG-1000 (Japanese Soda) and 34.5 parts of the corresponding polyin/anate compound (Takenate L1128 of Example 1) were further added to the mixture of Example 1 and reacted, and the same procedure as in Example 1 was carried out. A polyol compound (hereinafter referred to as POH-4) was obtained.

<Example 5> Polyisocyanate compound of Example 1 (Takenate L1
128) Example except that K was replaced with 90.7 parts of a polyisocyanate compound (number average molecular weight 1980, trade name Takenate L2710, manufactured by Narita Pharmaceutical Co., Ltd.) in which tolylene diiso7anate was condensed to both ends of polytetramethylene glycol. The experiment was conducted in the same manner as in 1. The obtained polyol compound is designated as POH-5.

<Example 6> Polyicanate compound of Example 1 (Tagane-4L1
128), diphenylmethane diisoquane)
11.4 parts and 54.2 parts of polypropylene glycol having a molecular weight of 1300 were added.

The diphenylmethanediyne/anate and polypropylene glycol react to form polyiso7anate. Thus, the polyol compound obtained in the same manner as in Example 1 was used as POII-6.0 <Example 7> Diol (BA-1o) of Example 1 was replaced with K, and ring-opening polymerization of E-caprolactone was carried out. The experiment was conducted in the same manner as in Example 1, except that 22.1 parts of a compound (number average molecular weight 530, trade name Plaxel 205, manufactured by Daicel Chemical Co., Ltd.) was added. The obtained polyol compound is designated as POH-7.

<Example 8> Polyicanate compound of Example 1 (Taganate L1
The experiment was carried out in the same manner as in Example 1 except that 89.7 parts of 128) was used, and the obtained polyol compound was designated as POH-8.

By increasing the amount of polyisocyanate compound, the molecular weight of polyol compound POH-8 increased rapidly.

<Example 9> Diol (molecular weight 396, trade name BA-4, Nippon Nyukazai Co., Ltd. Jj) in which about 4 molecules of ethylene glycol were added to both ends of ethylene and bisphenol A in place of the diol (BA-10) of Example 1. An experiment was conducted in the same manner as in Example 1 except for adding the tas portion. The obtained polyol compound is PO
Named H-9.

<Example 10> In place of the diol (BA-10) in Example 1, a diol in which about 8 molecules of propylene glycol were added to both ends of bisphenol A (molecular weight 660, trade name BAP-8) was used.
The experiment was conducted in the same manner as in Example 1, except that 27.5 parts of Nippon Nyukazai Co., Ltd.) were added. The obtained polyol compound is designated as poh-10.

<Example 11> In place of the diol (BA-10) of Example 1, 1,4-
The obtained polyol compound was added to POH-11 in the same manner as in Example 1 except that 3.7 parts of butanediol was added.
And so.

<Example 12> A polybutadiene compound having an average of 1.7 hydroxyl groups at the terminal, and 90% or more of butadiene units bonded by ■ and 2 (number average molecular weight 3,000°, trade name N1g5o)
50 parts of PB-3000 (manufactured by Nippon Soda Co., Ltd.) and 27.6 parts of the corresponding polyiso/anate compound (Takene L1128 of Example 1) were further added to the mixture of Example 9 and reacted. Similarly, the polyol compound (hereinafter referred to as POH-12) was added to one digit.

<Example 13> Polyiso/anate compound of Example 9 (Takene-4L1
A polyol compound (
(hereinafter referred to as POH-13) was obtained.

<Example 14> Polyisocyanate compound of Example 9 (Takenate L1
128) VC was changed and 11.4 parts of diphenylmethane diiso7anate and 41.7 parts of polytetramethylene glycol of molecule ztooo were added. This diphenylmethane diiso7anate and polytetramethylene glycol react to form polyiso7anate. Thus, a polyol compound obtained in the same manner as in Example 1 is designated as POH-14.

<Example 15> Diol (BA-10) K in Example 1 was replaced with 34.6 parts of a ring-opening polymer of ε-caprolactone (number average molecule i830, trade name Booksel 208, Daicel Chemical Co., Ltd.). The experiment was conducted in the same manner as in Example 1 except for the above. The obtained polyol compound is designated as POH-15.

<Example 16> An experiment was conducted in the same manner as in Example 9 except that the polyin 7-anate compound (Takenate L1128) was changed to 89.7 parts, and the obtained polyol compound was POH-
16.

By increasing the amount of polyisocyanate compound, the molecular weight of polyol compound POI(-16) increased rapidly.

(Characteristics table of polyol compounds The above polyol compounds POH-1 to 1 of Examples 1 to 16
6. 100 parts and 0.0 dipyltin 2 crates as a catalyst
2 parts were added, and the polyincanate compound of Example 1 (Takenate L1128) was blended so that the equivalent ratio of hydroxyl groups to isocyanate groups (NGOlo H) was 0.75.

(In the case of Example 1, 203.1 parts of polyol compound and 44.8 parts of polyiso7anate compound) This mixed liquid was coated on a polyester film and heated at 120°C for 10 minutes.
The adhesive tape was heated for 25 minutes to obtain an adhesive tape with an adhesive thickness of 25 μm. The physical properties of each adhesive tape are shown in the table.

<Examples 17 to 32> Polyol compounds in Examples 1 to 16 (POI(-
1 to 16) 60 parts of an aromatic-aliphatic copolymer petroleum resin (trade name: Tac Ace, manufactured by Mitsui Petrochemicals Co., Ltd.) that is non-reactive with icanate groups as a tackifier to 100 parts;
69 parts of dioctyl phthalate was added as a softener, and the mixture was heated and stirred until the tackifier was dissolved to obtain a transparent viscous liquid.

Next, in the same manner as in Examples 1 to 16, a polyyne/anate compound (Takenate L1128) was blended so that the equivalent ratio of hydroxyl groups to yn7anate groups (NGOloH) was 0.75, and 0.02 parts of diptyltin 2 crates were added. was added, coated on a soft vinyl chloride film, and heated at 120° C. for 10 minutes to obtain an adhesive tape with an adhesive thickness of 30 μm. Table H shows the physical properties of each adhesive tape.

<Comparative Example 1> The same polybutadiene compound (PBd-R45HT), diol (BA-10) and polyiso7anate compound (Takenate L1128) used in Example 1
were mixed as follows without polymerizing them in advance, with the blending ratios being the same as in Example 1, including the secondarily added polyisocyanate compound.

PBd-R45HT 100 copies BA-10
27.2 parts Takenate L1128 120.8 parts Diptyltin chloride 0.02 parts In this case, the equivalent ratio of hydroxyl groups to iso7anate groups (NGOloH) is 0.8
It became 75. Then, this liquid mixture was applied to a polyester film base material, and an adhesive tape was obtained in the same manner as in Example 1. Its adhesive properties are shown in Table H.

<Comparative Example 2> In addition to the formulation shown in Comparative Example 1, the polybutadiene compound (Nis+so PB-1000) 5 shown in Example 4 was added.
0 parts, polyincyanate compound (Takenate L112
8) 34.5 parts were added (same as the final blending ratio of Example 4) to obtain an adhesive tape in the same manner as Comparative Example 1.

<Comparative Example 3> Polybutadiene compound (PBd-R45HT) 100% was added to the same final blending ratio as shown in Example 5.
parts, diol (BA-10) 27.2 parts, polyino 7 anate compound (Takenate L2710) 90.7 parts, polyiso 7 anate compound (Takene 1-L1128) 4 parts
An adhesive tape was obtained in the same manner as in Comparative Example 1 by mixing 4.8 parts.

<Comparative Example 4> Same as the final blending ratio shown in Example 9, 100% K-naruyori polybutadiene compound (PBd-R45HT)
16.5 parts of diol (BA-4) and 120.8 parts of polyisocyanate compound (Takenate L1128) were mixed to obtain an adhesive tape in the same manner as in Comparative Example 1.

<Comparative Example 5> Polybutadiene compound (P B d -R45HT
) 100 parts, l, 4-butanediol polyinsyanate compound (Takene) L1128) 120, 8 parts were mixed to obtain an adhesive tape in the same manner as in Comparative Example 1 <Comparative Example 6> Shown in Example 15 Polybutadiene compound (PBd-R45HT) 10
0 parts, diol of ring-opening polymer of ξ-cuff rolactone (
A tape coated with 34.6 parts of Booksel 208) and a polyin 7-anate compound (Takenate L1128) was obtained.

As is clear from comparison with Examples 1 to 16, Comparative Examples 1 to 6 are inferior in each adhesive strength of Ic, SP adhesive strength, ball tack, and holding power.

<Comparative Example 7> A tackifier (Tac Ace) was dissolved in a softener (dioctyl phthalate), each compound was mixed to the final blending ratio in Example 17, and the mixture was spread on a soft vinyl chloride film. 0PBd-R45HT 10 was coated to obtain an adhesive tape in the same manner as in Example 17.
0 parts BA-1027, 2 parts Tac Ace 60 parts Dioctylphthalate 69 parts Takenate L1
128 120.8 parts Diptyltin laurate 002 parts <Comparative Example 8> An adhesive tape was obtained in the same manner as in Comparative Example 7 except that the final blending ratio was as in Example 25.

PBd-R45I (T 100 parts BA-
416, 5 parts Tac Ace 60 parts Dioctylphthalate 69 parts Takenate L1
128 120.8 parts Dibutyltin crate 0.02 parts Comparative Examples 7 and 8 were combined with Examples 17 to 128
As is clear from comparison with 32, both KS8P adhesive strength and ball tack adhesiveness are inferior.

<Comparative Example 9> A polybutadiene compound having an average of 1.7 hydroxyl groups at the terminal and 90 or more l,2-bonded butadiene units (number average molecular weight 1400, trade name N15ao)
PBG-1000, manufactured by Nippon Soda Co., Ltd.) 100 parts and polyisonoanate compound (Takene) Ll 12'8) 5
Two parts were mixed and reacted in the same manner as in Example 1 to obtain a polyol compound.

To 100 parts of this polyol compound, in the same manner as in Example 17, 60 parts of a tackifier (Tank Ace) and 69 parts of a softener (Dioctysiphthale-N) were added, and 31.2 parts of a polyisonoanate compound (Takenate L1128) was added with hydroxyl groups. It was blended so that the equivalent ratio of isocyanate groups (NGOloH) was 0.85, and 0.02 part of dibutyltin laurate was added and coated on a soft vinyl chloride film at 120°C.
The mixture was heated for 10 minutes to obtain an adhesive tape with an adhesive thickness of 30 pm.

Comparative Example 10> Polybutadiene compound (PBG'-toooo
), it has an average of 1.6 hydroxyl groups at the terminal, and l.

2-bonded butadiene compound (number average molecular weight 295
0, trade name N15so PBG-3000, manufactured by Nippon Soda Co., Ltd.) and 22.5 parts of a polyiso/anate compound (Takenate L1128) were mixed, and the same procedure as in Comparative Example 9 was carried out (polyisocyanate used secondarily). Compound(
15.7 parts of Takenate L1128) adhesive tape was obtained.

<Comparative Example 11> Polyincanate compound of Comparative Example 9 (Takenate L1
12B), add 31 parts of a polyincanate compound (number average molecular weight 1980, trade name Takenate L2710, manufactured by Kurade Pharmaceutical Co., Ltd.), and add 31 parts of a polyisocyanate compound (Takenate L1128) to be used secondarily. .2
(Equivalent ratio of hydroxyl group to icanate group (N
An adhesive tape was obtained in the same manner as in Comparative Example 9.

<Comparative Example 12> In Comparative Example 1O, 2G of a polyicanate compound (Takenate L2710) and 1 part of F were blended in place of the polyiso7anate compound (Takenate L1128), and the polyiso7anate compound (Takenate L1128) used secondarily was added. Takenate L
An adhesive tape was obtained in the same manner as in Comparative Example 9 using 18.8 parts of 1128).

The physical properties of the adhesive tapes of Comparative Examples 9 to 1 and 2 were compared to those of Examples 9 to 22.
It was confirmed that although the SP adhesive strength was the same, the ball tack and low-temperature development strength were inferior, making it particularly inconvenient to use at low temperatures.

In addition, in Comparative Examples 9 to 12, when the polymerized polyol compound and the polyyne/anate compound were reacted, the equivalent ratio of the water m groups and the ic anate groups (NGOlol(
) was 0.85, no assimilation of the reaction production region was observed.

(More than 1,000 units) Table ■ Physical properties of adhesive tape *If the base material is soft vinyl chloride, the base material will stretch and the holding power cannot be measured.

patent applicant Kansui Chemical Industry Co., Ltd. Representative: Mototoshi Fujinuma

Claims (1)

[Claims] 1) 60% by weight of 1.4-bonded butanoene units
The polyol component (A
) and the polyiso/anate compound (B), the equivalent ratio (NetloH) of the acidic anate group of the compound (@) to the hydroxyl group of the polyol component (A) is 0.2 to 0.65 K
The polyol compound (C) obtained by blending and reacting the polyol compound (C) and the polyic anate compound CD) as the main components, the equivalent ratio of the ic anate group of the compound (D) to the hydroxyl group of the compound (C) (N COlo ) I) is 0.
2) The polyol component (A) is characterized in that 1.4-bonded butadiene units account for 60 or more by weight, and the terminal The urethane adhesive according to claim 1, which contains 15% by weight or more of a polybutadiene compound (A) having a hydroxyl group and 3 to 10% by weight of a compound having an aromatic ring and two hydroxyl groups. Agent composition 3) Polybutadiene' compound (A') has a number average molecular weight of 1
4) The polyol compound (C) has a number average molecular weight s, oo
. 5) Innoanate of compound (D) Claims 1, 2, and 3 contain an aromatic or aromatic-aliphatic copolymer petroleum resin (E) that has no reactivity with groups.
Urethane pressure-sensitive adhesive composition according to item 6) 1,4-bonded butadiene units are 60% by weight-
The polyol component (A
) and the polyisocyanate compound (B), the equivalent ratio (N C010H) of the iso/anate group of the compound (B) to the hydroxyl group of the polyol component (A) is 0.2 to 0.65.
A compound (D) for the hydroxyl group of the compound (C) containing a polyol compound (C) obtained by blending and reacting so as to be 1C and a polyic anate compound (D) as main components.
The equivalence ratio of icanate groups (NGOloH) is 0.6
Use of a urethane pressure-sensitive adhesive composition characterized in that the urethane pressure-sensitive adhesive composition is applied to the surface of a base material and heated to cause the compound (C) and the compound CD) to react. Method 7) In the polyol component (A), 1.4-bonded butadiene units account for 60 weight ff 1% or more, and the polybutadiene compound (A) having a hydroxyl group at the terminal is 15 weight %.
Based on the above, the compound (A) having an aromatic ring and two hydroxyl groups is 3
8) Method of using the urethane pressure-sensitive adhesive composition according to claim 5, wherein the polyol compound (C) has a number average molecular weight of s, o
o. 30,000) and the average number of functional groups is 2 to 2.4. 9) Method for using the urethane pressure-sensitive adhesive composition according to claim 6 or 7. The urethane pressure-sensitive adhesive according to claim 6, 7, or 8, which contains an aromatic or aromatic-aliphatic copolymer petroleum resin (E) that has no reactivity with anate groups. How to use the composition