JP2003238936A - Adhesive - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an adhesive capable of easily and firmly fixing during the work for its strong adhesiveness and capable of easily peeling off after the work for its weak adhesiveness, in back grinding and dicing using an adhesive for fixing a precise part of a semiconductor, etc., and especially capable of being safely manufactured, transported, stored, and used. <P>SOLUTION: Using a gas generating agent, especially an organic azide compound, to this adhesive, under the condition of explosion propagation discriminant EP&lt;0, a decomposed gas is generated irradiating an electromagnetic wave such as a visible light, an ultraviolet ray, an X-ray, a &gamma;-ray, or an &alpha;-ray, especially an ultraviolet ray, to improve safety and also to facilitate a precision part peeled off the adhesive. <P>COPYRIGHT: (C)2003,JPO

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention is used, for example, for fixing a precision component or the like when polishing or cutting the precision component or the like in the process of manufacturing the precision component or the like.
Further, the present invention relates to a pressure-sensitive adhesive that is used, for example, for temporarily fixing an intermediate product, and is also used, for example, for release during coating.

[0002]

2. Description of the Related Art For example, in order to polish or cut a precision part, etc., the precision part or the like is attached to an adhesive tape in advance and fixed and polished, or cut with a rotary blade. After that, it is necessary to peel off each precision component from the adhesive tape and pick it up. When the above method is adopted, a strong fixing force (adhesive force) is required when pre-fixing precision parts etc. to the adhesive tape, and conversely weak adhesive force when picking up (easy peeling).
Is required.

Conventionally, in order to meet such demands, for example, in the field of fixing semiconductor wafers, ultraviolet rays (U
V) or an ultraviolet-curable adhesive tape (for example, Japanese Patent Laid-Open No. 1-272130) in which the adhesive strength is reduced by curing the adhesive layer by irradiation with ionizing radiation such as an electron beam, and water-soluble adhesive components. Adhesive tapes of the type that are eluted with warm water after processing using a polymer have been proposed. At present, the ultimate goal is to develop a pressure-sensitive adhesive whose pressure-sensitive adhesive force is completely zero at the time of pickup ("Industrial Materials", Vol. 43, No. 1, pp. 22-25, 1999).

In order to largely solve the above problems, the present inventor has made the invention disclosed in Japanese Patent Application Laid-Open No. 2001-200234, "Adhesive for fixing semiconductor wafer and processing method". An object of the invention is to provide a pressure-sensitive adhesive for fixing a semiconductor wafer, which is greatly improved in ease of peeling at the time of pickup, and is characterized in that a gas generating agent is used and the wafer is peeled by the generated gas.

[0005]

Gas generants are often reactive chemicals. The reactive substance is a substance that causes an exothermic reaction by self-reaction or by reacting with another substance. Some of these substances have the risk of fire and explosion. Therefore, it is important to develop the technology for improving the safety when the gas generating agent is mixed in the adhesive. An object of the present invention is to provide a safe pressure-sensitive adhesive that does not have a risk of fire or explosion, as a pressure-sensitive adhesive used in a wide field that generally requires easy peelability such as temporary fixing of precision parts. is there.

[0006]

The heat of reaction Q and the reaction start temperature T are considered as basic factors related to exothermic reactions such as fire and explosion. For example, in the transfer of a reactive substance, once the reactive substance generates a certain heat of reaction Q, the adjacent unreacted substance is heated to a temperature not lower than the reaction start temperature T to start the reaction, and one after another. Propagate. This is the explosive nature of reactive chemicals.

In the present invention, when a gas generating agent, which is a reactive substance, is added to an adhesive, the amount of the compound is adjusted to ensure safety during production, transportation, storage and use of the adhesive.
In order that the pressure-sensitive adhesive does not have the above-mentioned explosive property, it is preferable to make the explosive property determination function EP <0, which will be described later, and the pressure-sensitive adhesive thus obtained has no explosive property. The inventors have completed the invention by finding that they can exhibit excellent easy peeling properties.

Aspects of the present invention are as follows. (1) Adhesive that has easy peeling properties and is used in fields other than wafer fixing, and contains a gas generating agent that is a reactive chemical substance, and the content is not an explosive property. The above-mentioned pressure-sensitive adhesive. (2) A pressure-sensitive adhesive sheet-shaped or tape-shaped using a film-shaped substrate, containing a gas generating agent which is a reactive chemical substance, the content of which is not explosive. The above-mentioned pressure-sensitive adhesive. (3) The pressure-sensitive adhesive as described in (2) above, wherein the film-shaped base material transmits ultraviolet rays. (4) The pressure-sensitive adhesive as described in (2) or (3) above, wherein the pressure-sensitive adhesive layer has a thickness of 0.005 to 1 mm.

(5) The pressure-sensitive adhesive as described in any one of (1) to (4) above, wherein the content of the gas generating agent is the explosiveness judgment function EP <0. (6) The content of gas generant is RDX (Trimethylene
trinitramine) decomposition heat Q and decomposition reaction start temperature T, the explosiveness judgment function EP = logQ-0.38
The adhesive according to any one of (1) to (5) above, wherein EP <0 when the value of α is determined so that the value of × log (T-25) −1.67 + α becomes 0.45. . (7) The gas generating agent according to any one of (1) to (6) above, which generates gas by electromagnetic waves such as visible light, ultraviolet rays, X-rays, γ-rays, electron rays, or α-rays. Adhesive. (8) The pressure-sensitive adhesive as described in any of (1) to (7) above, wherein the gas generated from the gas generating agent is nitrogen gas.

(9) The pressure-sensitive adhesive as described in any of (1) to (8) above, wherein the gas generating agent contains a compound having an azide group. (10) The pressure-sensitive adhesive as described in (9) above, wherein the gas generating agent contains an organic compound having an azide group. (11) The pressure-sensitive adhesive as described in (10) above, wherein the gas generating agent contains an organic compound having a methyl azide group. (12) The pressure-sensitive adhesive according to any one of (1) to (12) above, wherein the pressure-sensitive adhesive contains an ultraviolet curable pressure-sensitive adhesive.

The present invention will be described in more detail below. In the present invention, all logarithms are common logarithms. As a method of simultaneously measuring the decomposition heat Q of the reactive substance and the decomposition reaction start temperature T using a small amount of sample, DS
C (differential scanning calorimetry) test method and DTA (differential thermal analysis)
Test methods are known. The explosiveness judgment function EP is expressed as a function of decomposition heat Q and decomposition start temperature T, and if the measured values of Q and T are less than 0, there is no explosiveness, and if 0 or more, there is explosiveness. It is the function to be judged.

This explosiveness judgment function EP is, for example, "Industrial Explosives" Vol. 48, No. 5 (Industrial Explosives Association 1987).
Pp. 311 to 315 "Prediction of Fire and Explosion Hazard of Reactive Chemical Substances (1st Report) Estimation of Explosive Properties of Self-Reactive Substances Using DSC Data" and "Reactive Chemistry" Material and safety of pyrotechnics "(Taisei Publishing Co., Ltd., Tadao Yoshida and Shozo Tamura, 1988), 104-
It is also introduced on page 105.

For example, the above-mentioned "Industrial Explosives" Vol. 48, No. 5
DSC for many reactive materials as described in
When the decomposition heat Q and the decomposition reaction start temperature T are measured using the test method, it is determined that the substance has an explosive property depending on where it is located on the coordinates with logQ as the vertical axis and log (T-25) as the horizontal axis. A non-explosive substance is clearly divided into two regions by one straight line. According to the above-mentioned “Industrial Explosives” Vol. 48, No. 5, this straight line is logQ = 0.38 × log
It is (T-25) +1.67. Substances above this line are explosive, and substances below this line are not explosive. Therefore, E = logQ-0.38 * log (T-25) -1.67 (Equation 1)
If P is less than 0, it is determined that there is no explosive property, and if P is 0 or more, it is determined that it is explosive.

As described in "Industrial Explosives" Vol. 48, No. 5, the reaction heat Q may be biased in the numerical value obtained by the measuring instrument or the measurer. Therefore, when the explosiveness determination method using the formula (1) is applied to any reactive substance, it is necessary to standardize Q and create a correct formula of EP. Regarding the standardization of this Q and the creation of the correct formula of EP, [Embodiment of the Invention]
As will be described later in, for example, it is performed as follows. That is, "Table. 1 Estimation of explosion propagation" published in "Industrial Explosives" Vol. 48, No. 5
and shock sensitivity from DSC data ”, RDX (Trimethylenetrinitramine, spec (MI
L-DTL-398D, type A)) is used as a standard. This substance is suitable as a reference substance because its specifications are clearly defined.

Using a DSC measuring device manufactured by Seiko Denshi Kogyo Co., Ltd., an aluminum container (pinhole) was used, and the measurement was repeated three times under the conditions of air atmosphere, 10 ° C./min, and sample amount of several mg. The values of the explosiveness judgment function EP of average are obtained by using the formula (1), and the obtained EP is obtained.
Value and EP value in the above "Table. 1" are compared, and "Tabl
Correct equation (1) so that it matches the value of EP in "e. 1". In the present invention, in order to allow the pressure-sensitive adhesive to contain the gas generating agent, the mixing ratio of the gas generating agent is set so that the content is the explosiveness judgment function EP
Within the range of 0, it is determined in consideration of the adhesive strength and the degree of easy peeling as necessary.

The value of EP is more preferably -0.5 to less than 0, and more preferably -0.25 to -0.01. As a gas generating agent, it generates gas by electromagnetic waves such as visible light, ultraviolet rays, X-rays, γ rays, or electron rays, or α rays so that mechanical and thermal loads are not applied to precision parts. There is no particular limitation as long as it is one. In particular, those that generate gas by ultraviolet rays are preferable. As such a gas generating agent, one containing a compound having an azide group is preferable. This is because the azido group decomposes and releases stable nitrogen molecules as a gas when it absorbs ionizing radiation, especially ultraviolet rays.

Vacuum ultraviolet rays, X rays, γ rays, and extremely high-energy β rays and α rays of electron rays, which have a very short wavelength among ultraviolet rays, often require careful handling as ionizing radiation.

In the present invention, a gas is generated by visible light or an electromagnetic wave having a shorter wavelength, which is not ionizing radiation but has a relatively high working energy, particularly an ultraviolet ray having a wavelength of 100 to 400 nm, especially an ultraviolet ray having a wavelength of 200 to 350 nm. Those that do are preferred. In particular, in the case of limiting the wavelength and carrying out a special application, the substance used for the gas generating agent may be subjected to absorbance measurement in advance and the wavelength near the absorption peak may be selectively used. In the case of an organic substance having a methyl azido group, the peak is 229.3 nm,
Since 284 nm exists, it can be effectively used.

The gas generating agent preferably contains a compound having an azide group. The azide group is an electromagnetic wave such as visible light, ultraviolet light, X-ray, γ-ray, or electron beam,
Alternatively, when it absorbs α rays, especially ultraviolet rays, it decomposes and releases stable nitrogen molecules as a gas. For compounds that have an azide group, AM Helmy et al. Described “20th Joint Propulsion Confe
rence (Ohio, 1984) "titled" Investigati
on of New Energetic Ingredient for Minimum Signatu
The azido group-containing organic compounds described in "1. Azide-substituted polyether prepolymer" on page 2, right column of the bulletin of "Re Propellants" and Table 5 on page 8 are known.

Particularly, an organic compound having an azide group is preferable because it can be easily homogenized when mixed with other components to form a sheet. In addition, since it decomposes without generating a heat load and generates gas, it does not affect the heat of other parts when processing precision parts, temporarily fixing them during assembly, or performing coating. preferable. In particular, an organic compound having a methylazido group is more preferable in terms of easiness of synthesis, handleability (safety) and the like. For example, GAP (Glycidy
l Azido Polymer), AMMO (3-azidomethyl-3 methyloxe
tane), BAMO (3,3-bis azidomethyl oxetane) and the like. In particular, for GAP, US Pat.
It can be produced by the synthetic method described in 8,450.

Examples thereof include hydroxy-terminated aliphatic polyethers represented by the following formula (A), for example, molecular weight =
About 2500, containing OH groups at both ends.

[0022]

[Chemical 1]

(However, x is 10 to 60, preferably 2
Is an integer from 0 to 40, R is-(CH2) nN3 or -CH2CHN3CH2
It is an alkyl azide group represented by N3, preferably a methyl azide group, and n is an integer of 1 to 5. )

Regarding the mechanism of the decomposition of an organic compound having a methyl azide group by ultraviolet rays, the present inventors have published the results of examination in terms of handling safety ("Industrial explosives", No. 5).
Volume 1, Issue 4 (Industrial Explosives Association, 1990) No. 240-
245). When the gas is released between the precision parts and the adhesive in this way, the contact area between the precision parts and the adhesive decreases, or the interfacial peeling is promoted by the gas pressure, which greatly improves the easy peelability of the adhesive. Can be improved.

The pressure-sensitive adhesive used in the present invention is not particularly limited as long as it is light-transmissive or electron-beam transmissive, particularly light-transmissive. For example, a rubber-based pressure-sensitive adhesive (polyisobutylene, Unsaturated rubber such as butyl rubber;
Ethylene-propylene (-diene) copolymer rubber, olefin block copolymer rubber, saturated rubber such as acrylic rubber), acrylic pressure-sensitive adhesive (copolymer of acrylic acid ester and functional group-containing monomer, etc.), photopolymerization -Type oligomer type pressure-sensitive adhesive (formed on the skeleton of polyether, polyester, epoxy resin, polyurethane, etc. As functional groups such as acryloyl group (CH2 = CHCO-), methacryloyl group (CH
It is preferable that two or more 2 = C (CH3) CO-) are added. Specific examples thereof include epoxy acrylate, polyether acrylate, polyester acrylate, urethane acrylate, and the like, which are known as typical ultraviolet curable resins. It is widely used as a protective coating for optical fibers and electric wires), a polyether adhesive, a polyester adhesive, a polyurethane adhesive, and the like.

Examples of the UV-curable adhesive include:
(A) Acrylic adhesive [copolymer of ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, hydroxymethyl acrylate, etc.] and / or polyether adhesive and / or polyester adhesive, and (b) photopolymerizable Oligomers (the above-mentioned UV curable resins; various oligomers such as urethane series, polyether series, polyester series, polycarbonate series, polybutadiene series)
And (c) if necessary, a photoinitiator (1-hydroxycyclohexyl phenyl ketone, isopropyl benzoin ether, benzophenone, xanthones, etc.) and (d) if necessary, a crosslinking agent (epoxy-based crosslinking agent, aziridine-based crosslinking agent, Examples thereof include those prepared by blending with an isocyanate-based crosslinking agent).

Further, the ultraviolet-curable adhesive contains (e)
Other UV-curable compounds such as polyacrylate of aliphatic polyol can be used in combination. The pressure-sensitive adhesive used in the present invention may be a three-dimensional network structure in which the pressure-sensitive adhesive layer is cured by irradiation with electromagnetic waves such as visible light, ultraviolet rays, X-rays, γ-rays, electron rays, or α-rays, especially ultraviolet rays. It is desirable to use an ultraviolet-curable pressure-sensitive adhesive capable of producing a resin and imparting appropriate flexibility.

As described above, generally, the UV-curable adhesive has a high adhesive force during processing such as polishing and dicing, and is cured by UV irradiation to reduce the adhesive force between the precision component and the adhesive tape. This is preferable because it is possible. The pressure-sensitive adhesive of the present invention is preferably provided in the form of a sheet or tape using a film-like substrate for practical use. Specifically, the base material is not particularly limited as long as it is a sheet-shaped or tape (film) -shaped rubber or thermoplastic resin having light transparency, but, for example, when the pressure-sensitive adhesive is cured by UV irradiation, UV transmission It is desirable to use a flexible sheet or tape (film).

For example, polyethylene, polypropylene,
Polyolefin film such as ethylene-propylene copolymer, ethylene-acrylic acid ester copolymer, ethylene-acrylic acid copolymer, ionomer, polybutene-1, ethylene-vinyl acetate copolymer, polyester film, polycarbonate film, PMMA A resin or rubber film having a light transmitting property such as a film can be used. When the pressure-sensitive adhesive of the present invention is formed into a sheet or a tape, the pressure-sensitive adhesive layer may be formed on a film made of an ultraviolet-transparent substrate, for example. It is desirable that the thickness of the base material is usually about 10 to 200 μm. At that time, the thickness of the pressure-sensitive adhesive layer is preferably 0.005 to 1 mm in order to effectively utilize the generated gas,
More preferably, it is 0.01 to 0.5 mm.

The method for processing precision parts and the like using the pressure-sensitive adhesive of the present invention, as described above, uses electromagnetic waves such as ultraviolet rays.
While the pressure-sensitive adhesive layer hardens and the adhesive strength decreases, it generates gas from the gas generating agent contained in the pressure-sensitive adhesive to peel off precision parts, etc. There are many advantages such as the fact that the equipment used can be used as it is. In the present invention, when the pressure-sensitive adhesive is subjected to electromagnetic waves such as visible light, ultraviolet rays, X-rays, γ-rays, electron rays, or α-rays, especially ultraviolet rays, the irradiation amount is the main base material of the UV-curable pressure-sensitive adhesive. It cannot be unconditionally defined because it varies depending on the type of the photopolymerizable oligomer to be added, the amount thereof, and the like, but in general, it is generally an electromagnetic wave such as visible light, ultraviolet rays, X-rays, γ-rays, or an electron beam to be irradiated.
Alternatively, about 10 seconds is sufficient by controlling the dose of α rays.

[0031]

BEST MODE FOR CARRYING OUT THE INVENTION Embodiments of the present invention will be described more specifically below. The following experiments were conducted to demonstrate the effect of the present invention. That is, the gas generation characteristics by ultraviolet irradiation when an azide group-containing compound was used as a gas generating agent in combination with various ultraviolet curable adhesives, and the gas generation characteristics by ultraviolet irradiation when used alone were verified.

Before conducting the verification experiments for the examples and comparative examples, the decomposition heat Q used for the explosiveness judgment function EP is as follows.
Table, published in the above "Industrial Explosives" Vol. 48, No. 5.
Normalization was performed using RDX, a substance in 1. With respect to this RDX, a DSC analysis was carried out with a DSC-220C manufactured by Seiko Denshi Kogyo Co., Ltd. (aluminum container pinhole, 10 ° C./min), the decomposition heat Q and the heat generation start temperature T were measured, and the α value was calculated. , EP values were obtained. First time T = 209.9 ° C. Q = 517 Cal / g EP = 0.18 Second time T = 210.7 ° C. Q = 522 Cal / g EP = 0.19 Third time T = 209.3 ° C. Q = 472 Cal / g EP = 0.14 The average EP was 0.17.

Regarding this value, the above-mentioned “industrial explosives” No. 48
Volume, T = 2, which is the value listed in Table 1 of No. 5 above.
By comparing with 14 ° C., Q = 968 Cal / g, EP = 0.45, and by correcting the above formula (1) in the positive direction of 0.28, Q was standardized and a correct formula of EP was prepared. About the difference of this Q value, "Industrial explosives" Vol.49,
No. 1 (Industrial Explosives Association 1988) pp. 47-52 "Prediction of fire / explosion risk of reactive chemical substances (2nd report)
In the “Comparative examination of multiple DSC and DTA data”, it was determined that the maximum Q value had a variation of about 2.5 times depending on the measurement, and it was determined that the correction accuracy was acceptable.

Therefore, in the following embodiments, the equation (1) is corrected and used as the following equation (2). EP = logQ-0.38 * log (T-25) -1.67 + 0.28 ... (2) Here, in case of EP = 0.45, alpha value = 0.28 was calculated. First, a GAP polymer was synthesized according to the disclosure of US Pat. No. 4,268,450. Through this example and comparative example, a GAP polymer (Glycidyl Azido Polyme) having a molecular weight of about 2,500 and OH groups at both ends was used as a gas generating agent.
r) was used.

[0035]

Example 1 A polyester polyol (7/3 mixture of ODX688 and 106) manufactured by Dainippon Ink and Chemicals, Inc. was used as an adhesive to the above GAP polymer, and GAP and 7/3, 5/5, respectively. The mixture was mixed at a ratio of 3/7 and the DSC measurement was performed. As a result, (a) GAP7
/ ODX3, T = 190.6 ° C., Q = 337 Cal
/ G, EP = 0.29, (b) GAP5 / ODX
In 5, T = 184 ° C., Q = 257 Cal / g, EP =
0.18, and (C) GAP3 / ODX7, T =
189.4 ° C., Q = 160 Cal / g, EP = −0.0
It became 3.

Therefore, GAP (polymer containing azido group)
In the case where the content ratio of (a) and (b) is more than 30% by weight (comparative example), the explosiveness judgment function EP> 0 and the explosiveness exists, whereas the content of GAP When the rate was (C) (30% or less; Example), the explosiveness judgment function EP <0 was established, and it was confirmed that there was no explosiveness.

[0037]

Example 2 The GAP3 / ODX used in Example 1
Fluoride resin sheet by uniformly mixing 8.6 g of IPDI (isophorone diisocyanate) and 3.4 g of TPA-100 (adduct of hexamethylene diisocyanate (manufactured by Asahi Kasei Co., Ltd.)) with 100 g of the composition (C) of 7 It was thinly spread (about 2.4 mm thick) on a substrate and heated at 60 ° C. to cure. After cooling to room temperature, a glass plate was placed on and adhered to produce a pressure-sensitive adhesive.

In this case, as compared with the case (c) of Example 1, since a curing agent or the like is added to the polyester polyol polymer (ODX7) as an adhesive, the content of GAP should be lower than 30%. Therefore, it is expected that the explosiveness judgment function EP <0 and that there is no explosiveness, and the following experiment supports the fact. In this state, the adhesive was irradiated with ultraviolet rays (115V, 60Hz, 0.16A), and the state of the adhesive was observed. As a result, after a few ten minutes, the adhesion surface was partially peeled off by the gas generated from the inside. It came to the surface.

It should be noted that the fluororesin sheet was used for releasing the mold in this example. However, the interface between the fluororesin sheet and the polymer cured product was the glass plate (18 ×) used in this experiment. The peeling was larger than 18 mm). The number of bubbles generated is 1 square cm and a dozen or more (most of them have a diameter of about 1 to 2 mm), and the generated gas has high uniformity of dispersibility of the organic azide. It was confirmed that a large amount occurred at the interface between the polymer, the glass plate and the fluororesin sheet, and was extremely effective for the purpose of the present invention.

Through this experiment, it was confirmed that it is preferable that the pressure-sensitive adhesive layer has a thickness of 1 mm or less for bubble formation.
It was confirmed that the generated gas can be effectively used for interfacial peeling by forming a polymer cured product (adhesive) layer with a thickness of 1 mm or less.

[0041]

Comparative Example 1 The GAP polymer used in Example 1 was spread flat (about 3 mm), a microscope cover glass plate (18 × 18 mm) was placed on the top, and ultraviolet irradiation was performed from the top as in Example 2. . As a result, it was confirmed that many bubbles presumed to be nitrogen gas were generated between the glass plate and the polymer. In this case, the content of GAP polymer is 10
It becomes 0%.

Next, a DSC analysis of this substance was carried out with a DSC-220C manufactured by Seiko Denshi Kogyo Co., Ltd. (pinhole, 10 ° C./min), the decomposition heat Q and the heat generation start temperature T were measured, and EP was obtained. . As a result, Q = 568 Cal / g, T
= 181.5 ° C., EP = 0.53, EP> 0
Therefore, it was judged that there was an explosive property.

[0043]

Comparative Example 2 GAP polymer 100 used in Example 1
3.6 g of IPDI (isophorone diisocyanate)
And TPA-100 (adduct of hexamethylene diisocyanate (Asahi Kasei Co., Ltd.)) (8.7 g) were added, uniformly mixed, and then spread thinly, and heated at about 60 ° C. to cure,
In that state, a glass plate was put on and closely adhered. In that state, ultraviolet rays were irradiated in the same manner as in Comparative Example 1, and the state was observed.
After a few minutes, the adhesion surface was peeled off by the gas generated from the inside and partly floated. In this case, G
Since a curing agent and the like are added to the AP polymer, the content of the GAP polymer is calculated to be 89%, which is 30 in Example 1.
Greatly exceeds the critical value of%.

DSC measurement of this cured product was carried out, and Q = 4
90 Cal / g, T = 182 ° C. were obtained. EP = 0.50
It was judged that there was an explosive property.

[Discussion] From the results of Comparative Examples 1 and 2, in order to increase (cure) the viscosity of the pressure-sensitive adhesive, IPDI (isophorone diisocyanate), TPA-100 (hexamethylene diisocyanate adduct (manufactured by Asahi Kasei Corporation) It can also be seen that the inclusion of) further reduces the explosiveness judgment function EP.

[0046]

Comparative Example 3 After the GAP polymer used in Example 1 was irradiated with ultraviolet rays at a content rate of 50% (corresponding to (b) in Example 1),
A confirmation test on whether or not the gas generating agent has a peeling property was performed for APR resin (photosensitive resin, carboxylic acid-modified polyurethane resin) manufactured by Asahi Kasei Co., Ltd.
The mixture was mixed at a ratio of 0:50, thinly spread in the same manner as in Comparative Example 2, a glass plate was placed, and ultraviolet rays were irradiated. In that case, G
The content of AP polymer is 50% of APR resin in addition to polyester polyol polymer (ODX5) as an adhesive.
Therefore, the value should be close to the GAP critical value of 30% in the first embodiment.

As a result, gas generation was observed during and after the curing of the polymer. Then, as a result of exposing to sunlight (visible light) for about 30 minutes, partial peeling of the glass plate and the polymer was observed, and it was possible to easily remove it by applying force by hand. However, the mixture was from 77 ° C to 61 Cal.
/ G, 178 ° C to 173 Cal / g, 287 ° C to 1
Since heat generation of 23 Cal / g was observed, the EP was judged to be 0.31, that is, EP> 0, and the result was that there was an explosive property. This result shows that the APR resin used is 308 ° C.
It was inferred that the heat generation was caused by the fact that it affected the explosive property.

[0048]

Comparative Example 4 In the same manner as in Comparative Example 3, the GAP polymer used in Example 1 was tested using PPG (polypropylene glycol) instead of the APR resin. The glass plate and the polymer were hardened while being in close contact, and it was unlikely that they could be removed by hand without breaking the glass plate.

[0049]

As described above, according to the present invention, in the process of manufacturing precision parts such as semiconductors, gas is generated in the adhesive as an adhesive for temporarily fixing or coating. By including the agent, after fixing precision parts etc. and polishing or dicing,
It is very easy to peel off the precision parts and / or temporarily fix the intermediate products and the like, and to release the mold after coating.

Further, in the present invention, by using an organic azide compound or the like as the gas generating agent, it is irradiated with electromagnetic waves such as visible light, ultraviolet rays, X-rays, γ-rays, electron rays, or α-rays, especially ultraviolet rays. In some cases, emits gas,
It is extremely easy to peel off precision parts without applying mechanical or thermal load. In particular, in the present invention, it was found that when a reactive chemical substance is contained, the peeling effect of precision parts and the like appears even at a low content rate such that the explosiveness judgment function EP <0, and the safety is improved. It is a thing.

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[Procedure amendment]

[Submission date] July 26, 2002 (2002.7.2)
6)

[Procedure Amendment 1]

[Document name to be amended] Statement

[Name of item to be amended] Claims

[Correction method] Change

[Correction content]

[Claims]

[Procedure Amendment 2]

[Document name to be amended] Statement

[Correction target item name] 0010

[Correction method] Change

[Correction content]

(9) The pressure-sensitive adhesive as described in any of (1) to (8) above, wherein the gas generating agent contains a compound having an azide group. (10) The pressure-sensitive adhesive as described in (9) above, wherein the gas generating agent contains an organic compound having an azide group. (11) The pressure-sensitive adhesive as described in (10) above, wherein the gas generating agent contains an organic compound having an azidomethyl group . (12) The pressure-sensitive adhesive according to any one of (1) to (12) above, wherein the pressure-sensitive adhesive contains an ultraviolet curable pressure-sensitive adhesive.

[Procedure 3]

[Document name to be amended] Statement

[Correction target item name] 0018

[Correction method] Change

[Correction content]

In the present invention, a gas is generated by visible light or an electromagnetic wave having a shorter wavelength, which is not ionizing radiation but has a relatively high working energy, particularly an ultraviolet ray having a wavelength of 100 to 400 nm, especially an ultraviolet ray having a wavelength of 200 to 350 nm. Those that do are preferred. In particular, in the case of limiting the wavelength and carrying out a special application, the substance used for the gas generating agent may be subjected to absorbance measurement in advance and the wavelength near the absorption peak may be selectively used. In the case of an organic substance having an azidomethyl group , the peak is 229.3 nm,
Since 284 nm exists, it can be effectively used.

[Procedure amendment 4]

[Document name to be amended] Statement

[Correction target item name] 0020

[Correction method] Change

[Correction content]

Particularly, an organic compound having an azide group is preferable because it can be easily homogenized when mixed with other components to form a sheet. In addition, since it decomposes without generating a heat load and generates gas, it does not affect the heat of other parts when processing precision parts, temporarily fixing them during assembly, or performing coating. preferable. In particular, an organic compound having an azidomethyl group is more preferable in terms of easiness of synthesis and handling (safety). For example, GAP (Glycidy
l Azido Polymer), AMMO (3-azidomethyl-3 methyloxe
tane), BAMO (3,3-bis azidomethyl oxetane) and the like. In particular, for GAP, US Pat.
It can be produced by the synthetic method described in 8,450.

[Procedure Amendment 5]

[Document name to be amended] Statement

[Name of item to be corrected] 0023

[Correction method] Change

[Correction content]

(However, x is 10 to 60, preferably 2
Is an integer from 0 to 40, R is-(CH ₂ ) n N ₃ or -CH ₂ CHN ₃ CH
Alkyl azide groups represented by ₂ N _3, preferably Ajidome
It is a chill group , and n is an integer of 1 to 5. )

[Procedure correction 6]

[Document name to be amended] Statement

[Name of item to be corrected] 0024

[Correction method] Change

[Correction content]

Regarding the mechanism of decomposition of an organic compound having an azidomethyl group by ultraviolet rays, the present inventors have published the result of examination in terms of handling safety (“Industrial explosive”, No. 5).
Volume 1, Issue 4 (Industrial Explosives Association, 1990) No. 240-
245). When the gas is released between the precision parts and the adhesive in this way, the contact area between the precision parts and the adhesive decreases, or the interfacial peeling is promoted by the gas pressure, which greatly improves the easy peelability of the adhesive. Can be improved.

Claims (12)

[Claims] 1. A versatile pressure-sensitive adhesive having easy peeling property, containing a gas generating agent which is a reactive chemical substance, and the content thereof is an amount having no explosive property. The adhesive. 2. A pressure-sensitive adhesive sheet-shaped or tape-shaped using a film-shaped base material, containing a gas generating agent which is a reactive chemical substance, the content being not explosive The adhesive is characterized in that the amount is 3. The pressure-sensitive adhesive according to claim 2, wherein the film-shaped substrate is transparent to ultraviolet rays. 4. The pressure-sensitive adhesive according to claim 2, wherein the pressure-sensitive adhesive layer has a thickness of 0.005 to 1 mm. 5. The explosiveness judgment function E is determined by the content of the gas generant.
The pressure-sensitive adhesive according to claim 1, wherein P <0. 6. The content of the gas generating agent is RDX (Trimet
(Hylenetrinitramine) decomposition heat Q and decomposition reaction start temperature T
For the measured value of, the explosiveness judgment function EP = logQ−
When the value of α is determined so that the value of 0.38 × log (T-25) −1.67 + α becomes 0.45, EP <0
The pressure-sensitive adhesive according to any one of claims 1 to 5. 7. The gas generating agent is visible light, ultraviolet light, X-ray,
The pressure-sensitive adhesive according to any one of claims 1 to 6, which generates a gas by electromagnetic waves such as γ rays, electron rays, or α rays. 8. The pressure-sensitive adhesive according to claim 1, wherein the gas generated from the gas generating agent is nitrogen gas. 9. The pressure-sensitive adhesive according to claim 1, wherein the gas generating agent contains a compound having an azide group. 10. The pressure-sensitive adhesive according to claim 9, wherein the gas generating agent contains an organic compound having an azide group. 11. The pressure-sensitive adhesive according to claim 10, wherein the gas generating agent contains an organic compound having a methyl azide group. 12. The pressure-sensitive adhesive according to claim 1, wherein the pressure-sensitive adhesive contains an ultraviolet curable pressure-sensitive adhesive.