CN111793152A

CN111793152A - Photoinitiator composition and application thereof

Info

Publication number: CN111793152A
Application number: CN202010775679.7A
Authority: CN
Inventors: 张程
Original assignee: Individual
Current assignee: Individual
Priority date: 2020-08-05
Filing date: 2020-08-05
Publication date: 2020-10-20

Abstract

The invention discloses a photoinitiator composition and application thereof, relates to the technical field of photoinitiators, and can be used for adhesive reducing tapes.

Description

Photoinitiator composition and application thereof

Technical Field

The invention relates to the technical field of photoinitiators, and particularly relates to a photoinitiator composition and application thereof.

Background

Semiconductor processing elements such as wafers, chips and the like are subjected to processes such as grinding, cutting and the like in production, wherein the workpieces are fixed by using adhesive tapes, certain protection is provided for the workpieces, the workpieces are prevented from being cracked in the processing process, and the adhesive tapes are removed after the grinding or cutting is finished so as to perform the next step of operation. When the adhesive tape is removed, the adhesive tape has a high viscosity, and the adhesive tape often remains on the surface of the workpiece, which results in a decrease in product yield.

In order to reduce the residual glue phenomenon, the semiconductor processing industry uses a UV adhesive tape, and the related technology can refer to chinese patent CN 206256021U, and by adding a photoinitiator into an adhesive, the adhesive is polymerized under UV irradiation, and then the viscosity is reduced, so that the adhesive tape is easier to be peeled off from a workpiece, however, the photoinitiator on the market at present is difficult to meet the use requirement of the adhesive tape, i.e. the viscosity of the adhesive is rapidly and stably reduced, and no residual glue is left.

Disclosure of Invention

In order to solve the above problems, a first aspect of the present invention provides a photoinitiator composition comprising at least two compounds a containing a cation represented by formula 1, formula 1:

wherein m and n are respectively and independently selected from integers not less than 9; the molar mass of the cation is not less than 550 g/mol.

As a preferred technical scheme, m and n are respectively and independently selected from integers not less than 10; the molar mass of the cation is not less than 570 g/mol.

As a preferable technical scheme, m and n are respectively and independently selected from integers between 11 and 13; the molar mass of the cation is not less than 580 g/mol.

As a preferred technical scheme, the composition also comprises acetonitrile; the acetonitrile accounts for 1-10 wt% of the composition.

As a preferable technical scheme, the acetonitrile accounts for 3-8 wt% of the composition.

As a preferable technical scheme, the acetonitrile accounts for 4-6 wt% of the composition.

As a preferred technical scheme, the composition also comprises (1-methyl decyl) -benzene.

As a preferred technical scheme, the composition also comprises 1, 2-diiodo-4, 5-dimethylbenzene.

As a preferred technical scheme, the composition also comprises 2- (2-iodophenyl) -2, 3-dihydro-1H-naphtho [1, 2-e ] [1, 3] oxazine.

A second aspect of the invention provides the use of a photoinitiator composition as described above for a tack-reducing or tack-reducing film.

Has the advantages that: the invention provides a photoinitiator composition which can be used for an adhesive reducing tape, and diaryliodonium salts with higher photoinitiation efficiency are improved, so that the diaryliodonium salts still have higher photosensitivity to ultraviolet light in a wider wavelength range, polymerization reaction can be initiated in a short time, and the adhesive reducing tape can be quickly stripped from the surface without residual adhesive.

Drawings

To further illustrate the benefits of a photoinitiator composition and its use provided herein, the accompanying drawings are provided, and it is noted that the drawings provided herein are merely selected examples of all drawings, and are not intended to be limiting of the claims, and that all other corresponding figures obtained from the drawings provided herein are to be considered within the scope of the present application.

FIG. 1 is an IR spectrum of example 1, which contains the characteristic information of benzene ring compounds.

FIG. 2 is a NMR spectrum of example 1 of the present invention.

FIG. 3 is a GC-MS test spectrum of example 1 of the present invention.

FIG. 4 shows the analysis result of an unknown component in example 1 of the present invention, which is (1-methyldecyl) -benzene.

FIG. 5 shows the analysis result of an unknown component in example 1 of the present invention, which indicates that it is 1, 2-diiodo-4, 5-dimethylbenzene.

FIG. 6 shows the analysis result of an unknown component in example 1 of the present invention, which indicates that it is 2- (2-iodophenyl) -2, 3-dihydro-1H-naphtho [1, 2-e ] [1, 3] oxazine.

Detailed Description

The invention will be further understood by reference to the following detailed description of preferred embodiments of the invention and the examples included therein. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this application belongs. To the extent that a definition of a particular term disclosed in the prior art is inconsistent with any definitions provided herein, the definition of the term provided herein controls.

As used herein, a feature that does not define a singular or plural form is also intended to include a plural form of the feature unless the context clearly indicates otherwise. It will be further understood that the term "prepared from …," as used herein, is synonymous with "comprising," including, "comprising," "having," "including," and/or "containing," when used in this specification means that the recited composition, step, method, article, or device is present, but does not preclude the presence or addition of one or more other compositions, steps, methods, articles, or devices. Furthermore, the use of "preferred," "preferably," "more preferred," etc., when describing embodiments of the present application, is meant to refer to embodiments of the invention that may provide certain benefits, under certain circumstances. However, other embodiments may be preferred, under the same or other circumstances. In addition, the recitation of one or more preferred embodiments does not imply that other embodiments are not useful, nor is it intended to exclude other embodiments from the scope of the invention.

The diaryl iodonium salt serving as a cationic photoinitiator is decomposed into Lewis acid and free radicals under the action of light, and the Lewis acid can further react to obtain strong protonic acid, so that the diaryl iodonium salt can initiate cationic photopolymerization and free radical photopolymerization, and has high initiation efficiency, but the diaryl iodonium salt has low utilization rate of an ultraviolet light source because the main absorption wavelength of the diaryl iodonium salt is 200-250 nm, so that the application of the diaryl iodonium salt is limited. The present inventors have focused on a photoinitiator composition comprising a diaryliodonium salt, and have conducted intensive studies on the viscosity reducing effect of a diaryliodonium salt having a long carbon chain in a UV viscosity reducing agent, and as a result, have found that when a single type of a long carbon chain diaryliodonium salt is used as a photoinitiator, a sufficiently satisfactory viscosity reducing effect cannot be obtained, and that even if the viscosity reducing effect is provided, the effect is unstable. Further, as a result of further intensive studies, it was found that, on the one hand, the ultraviolet light source cannot efficiently excite the diaryliodonium salt to be converted into an excited state, and thus the viscosity reducing effect is not satisfactory, and on the other hand, the counter anion generated after dissociation of the diaryliodonium salt has a weak nucleophilicity and is hard to form a covalent bond with the active center of the chain-extending chain, thereby terminating the reaction.

To solve the above problems, a first aspect of the present invention provides a method of manufacturing a semiconductor deviceA photoinitiator composition comprising at least two compounds a containing a cation according to formula 1, formula 1:

In some preferred embodiments, m and n are each independently selected from integers not less than 10; the molar mass of the cation is not less than 570 g/mol; more preferably, m and n are respectively and independently selected from integers between 11 and 13; the molar mass of the cation is not less than 580 g/mol.

In some preferred embodiments, the anion of compound a is selected from tetrafluoroborate ion (BF)₄ ^-) Perchlorate ion (ClO)₄ ^-) Fluorosulfonate ion (FSO)₃ ^-) Hexafluorophosphate ion (PF)₆ ^-) Hexafluoroarsenate ion (AsF)₆ ^-) Hexafluoroantimonate ion (SbF)₆ ^-) Triflate ion (CF)₃SO₃ ^-) Tetraphenylborate ion (Ph)₄B^-) One kind of (1).

Examples of compound a include, but are not limited to, the chemical formulas shown in formula 2 to formula 9:

formula 2:

the molar mass of the cation is 617 g/mol;

formula 3:

the molar mass of the cation is 589 g/mol;

formula 4:

the molar mass of the cation is 603 g/mol;

formula 5:

the molar mass of the cations is 631 g/mol;

formula 6:

the molar mass of the cation is 617 g/mol;

formula 7:

the molar mass of the cation is 589 g/mol;

formula 8:

the molar mass of the cation is 617 g/mol;

formula 9:

the molar mass of the cations was 631 g/mol.

In some preferred embodiments, the composition comprises four compounds a, which are represented by formula 2, formula 3, formula 4, and formula 5.

In some preferred embodiments, the composition comprises four compounds a, each of which is represented by formula 2, formula 3, formula 4, formula 5, in a weight ratio of 1: (0-0.2): (0-0.2): (0-0.2) except 0.

The combination of the four compounds A improves the utilization effect of diaryl iodonium salt on ultraviolet light, so that the viscosity of an anti-adhesive or anti-adhesive film is reduced rapidly under short-time UV irradiation, and the reason is presumed that a carbon chain with a certain length can be used as an electron supply group, the electron cloud density of a benzene ring is improved, the iodonium salt is excited more easily, the absorbable wavelength is red-shifted, the carbon chains with different lengths have slightly different influences on the electron cloud density of the benzene ring, the number of energy level layers between the ground state and the excited state of the diaryl iodonium salt is increased, the activity of the excited state iodonium salt on different energy levels is higher, and a series of continuous transitions are further caused. It should be noted, however, that the longer the carbon chain, the stronger the electron-donating ability of the substituent on the benzene ring, and the higher the photosensitivity of the iodonium salt, but accordingly, the weaker the interaction between the dissociated anion and the active center of the chain-lengthening chain, and the less the initiated polymerization reaction proceeds, so that the control of the carbon chain length and the ratio between iodonium salts having different substituents is required, wherein the control of the ratio between different iodonium salts not only can increase the degree of progress of the polymerization reaction, but also can adjust the photosensitivity of the photoinitiator, so that the anti-adhesive or anti-adhesive film can be removed in a short time without leaving adhesive residues.

In the present application, the compound a may be commercially available or synthetically obtained, and its preparation method may be any one known to those skilled in the art, for example, refer to "preparation of 4, 4-didodecylbenziodonium hexafluoroantimonate" (image science and photochemistry, 3.2008, volume 26, phase 2, author: liu anchang, etc.), when preparing the compound a in the present application, corresponding preparation raw materials may be selected according to the structure of the compound a, including long-chain alkylbenzene, potassium iodate, potassium salt or sodium salt corresponding to anion, etc.

From the viewpoint of further improving the photosensitivity of the photoinitiator composition and promoting the polymerization reaction, in some preferred embodiments, the composition further comprises acetonitrile, the acetonitrile accounts for 1-10 wt% of the composition, and the balance is compound a; more preferably, the acetonitrile accounts for 3-8 wt% of the composition, and the balance is compound A; furthermore, the acetonitrile accounts for 4-6 wt% of the composition, and the balance is the compound A.

The invention can further improve the performance of the viscose reducing agent by adding acetonitrile, and the reason is that-CN group in the acetonitrile has nucleophilicity due to uneven electron cloud distribution, when anion in the iodonium salt is not enough to prolong polymer chain segment, the acetonitrile can be used as a nucleophilic reagent to continue the polymerization reaction, and simultaneously, when the acetonitrile is added into the polymerization reaction, the unsaturation degree and the branched chain structure in the system can be increased, so that the crosslinking density in the viscose reducing agent is increased, and the viscose reducing agent can be more easily stripped from the attached surface.

In some embodiments, (1-methyldecyl) -benzene (CAS number: 4536-88-3) is also included in the composition.

In some embodiments, 1, 2-diiodo-4, 5-dimethylbenzene (CAS number: 182-67-2) is also included in the composition.

In some embodiments, the composition further comprises 2- (2-iodophenyl) -2, 3-dihydro-1H-naphtho [1, 2-e ] [1, 3] oxazines (shown in formula 10).

Formula 10:

in some embodiments, the (1-methyldecyl) -benzene, 1, 2-diiodo-4, 5-dimethylbenzene, 2- (2-iodophenyl) -2, 3-dihydro-1H-naphtho [1, 2-e ] [1, 3] oxazine are impurities contained in the composition, each in an amount not exceeding 5ppm in the composition.

Ppm in this application means the impurities comprise parts per million by mass of the composition.

The (1-methyl decyl) -benzene in the invention can be an impurity which is isomerized by unreacted reactants in the preparation process of the compound A under the condition of strong acid; 1, 2-diiodo-4, 5-dimethylbenzene can be impurities obtained by further reacting with iodine-containing substances after a long-chain substituent group in long-chain alkylbenzene is attacked and broken by a free radical or other active groups; 2- (2-iodophenyl) -2, 3-dihydro-1H-naphtho [1, 2-e ] [1, 3] oxazines may be impurities which are obtained by reaction with other precursor impurities in the presence of acetonitrile. In the preparation process of the photoinitiator composition, the content of the impurities is reduced as much as possible, and the phenomenon that the performance of the viscose reducing agent is not up to the standard due to excessive conversion of effective substances into the impurities is avoided.

The present inventors have conducted intensive studies on a purification method of a diaryliodonium salt, and as a result, have developed a method for producing a high-purity diaryliodonium salt, in which the diaryliodonium salt obtained is recrystallized in an acetonitrile solvent in addition to a known method for synthesizing the diaryliodonium salt, thereby reducing impurities in the diaryliodonium salt and further reducing the content of the impurities in a photoinitiator composition.

In some embodiments, the photoinitiator composition is prepared by physical mixing.

Examples

The technical solution of the present invention is described in detail by the following examples, but the scope of the present invention is not limited to the examples. Unless otherwise specified, the starting materials in the present invention are all commercially available.

Example 1

Embodiment 1 provides a photoinitiator composition comprising a compound a represented by formula 2, formula 3, formula 4, formula 5, and the weight ratio between the four is 1: 0.1: 0.05: 0.05; the composition also includes acetonitrile 5 wt%, with the balance being compound a.

In this example, the compound A was synthesized by a known method and then recrystallized in an acetonitrile solvent.

Through detection and analysis, the composition contains impurities: (1-methyldecyl) -benzene 25ppm, 1, 2-diiodo-4, 5-dimethyl benzene 10ppm, 2- (2-iodophenyl) -2, 3-dihydro-1H-naphtho [1, 2-e ] [1, 3] oxazine 4 ppm.

Example 2

Embodiment 2 provides a photoinitiator composition comprising a compound a of formula 2; the composition also includes acetonitrile 5 wt%, with the balance being compound a.

Through detection and analysis, the composition contains impurities: (1-methyldecyl) -benzene 18ppm, 1, 2-diiodo-4, 5-dimethyl benzene 8ppm, 2- (2-iodophenyl) -2, 3-dihydro-1H-naphtho [1, 2-e ] [1, 3] oxazine 2 ppm.

Example 3

Embodiment 3 provides a photoinitiator composition, which includes a compound a shown in formula 2 and formula 3, and the weight ratio of the compound a to the compound a is 1: 0.2; the composition also includes acetonitrile 5 wt%, with the balance being compound a.

Through detection and analysis, the composition contains impurities: (1-methyldecyl) -benzene 21ppm, 1, 2-two iodine-4, 5-two methyl benzene 8ppm, 2- (2-iodine phenyl) -2, 3-two hydrogen-1H-naphtho [1, 2-e ] [1, 3] oxazine 3 ppm.

Example 4

Embodiment 4 provides a photoinitiator composition, including a compound a represented by formula 2, formula 4, formula 5, and the weight ratio between the four is 1: 0.1: 0.1; the composition also includes acetonitrile 5 wt%, with the balance being compound a.

Through detection and analysis, the composition contains impurities: (1-methyldecyl) -benzene 23ppm, 1, 2-diiodo-4, 5-dimethyl benzene 9ppm, 2- (2-iodophenyl) -2, 3-dihydro-1H-naphtho [1, 2-e ] [1, 3] oxazine 3 ppm.

Example 5

Embodiment 5 provides a photoinitiator composition comprising a compound a represented by formula 2, formula 3, formula 4, formula 5, and the weight ratio between the four is 1: 0.1: 0.05: 0.05.

Through detection and analysis, the composition contains impurities: 24ppm of (1-methyldecyl) -benzene and 11ppm of 1, 2-diiodo-4, 5-dimethylbenzene.

Example 6

Embodiment 6 provides a photoinitiator composition comprising a compound a represented by formula 2, formula 3, formula 4, formula 5, and the weight ratio between the four is 1: 0.1: 0.05: 0.05; the composition also includes acetonitrile 5 wt%, with the balance being compound a.

The compound A described in this example was synthesized according to known methods.

Through detection and analysis, the composition contains impurities: (1-methyl decyl) -benzene 72ppm, 1, 2-two iodine-4, 5-two methyl benzene 34ppm, 2- (2-iodine phenyl) -2, 3-two hydrogen-1H-naphtho [1, 2-e ] [1, 3] oxazine 15 ppm.

Evaluation of Performance

Under the initiation action of benzoyl peroxide, the ratio of 1: 4: 0.8: 2: 0.2 of acrylate monomers of isooctyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, acrylic acid and hydroxyethyl acrylate to prepare the acrylate pressure-sensitive adhesive, mixing the prepared acrylate pressure-sensitive adhesive with the photoinitiator composition in the embodiment 1-6, wherein the addition amount of the photoinitiator composition is 2 wt% of the pressure-sensitive adhesive, coating the pressure-sensitive adhesive on a PVC film to prepare the adhesive tape, wherein the coating thickness is 50 mu m, and testing the viscosity reduction performance of the adhesive tape.

The viscosity reducing performance test method comprises the following steps: the tape was adhered to a plastic plate, the peel strength of the tape before and after irradiation with an ultraviolet lamp was measured according to the method described in GB/T2790-1995 "test method for 180 ℃ peel strength of adhesive versus rigid Material", the rate of change in peel strength was recorded and the presence or absence of adhesive residue was observed, and the results are shown in Table 1. The rate of change of the peel strength was 100% (before irradiation/after irradiation/before irradiation), and the tape was irradiated with an ultraviolet lamp at two wavelengths of 254nm and 365nm, with an irradiation distance of 15cm and an irradiation time of 2 min.

TABLE 1

According to embodiments 1 to 6, the present invention provides a photoinitiator composition, which can be used for an adhesive reducing tape, has high photosensitivity to ultraviolet light in a wide wavelength range, and can initiate a polymerization reaction in a short time, so that the adhesive reducing tape can be rapidly peeled off from a surface without leaving residual adhesive.

The foregoing examples are merely illustrative and serve to explain some of the features of the method of the present invention. The appended claims are intended to claim as broad a scope as is contemplated, and the examples presented herein are merely illustrative of selected implementations in accordance with all possible combinations of examples. Accordingly, it is applicants' intention that the appended claims are not to be limited by the choice of examples illustrating features of the invention. Also, where numerical ranges are used in the claims, subranges therein are included, and variations in these ranges are also to be construed as possible being covered by the appended claims.

Claims

1. A photoinitiator composition comprising at least two compounds a, wherein the compounds a comprise a cation according to formula 1, formula 1:

2. The photoinitiator composition according to claim 1 wherein m and n are each independently selected from the group consisting of integers not less than 10; the molar mass of the cation is not less than 570 g/mol.

3. The photoinitiator composition according to claim 2 wherein m and n are each independently selected from integers ranging from 11 to 13; the molar mass of the cation is not less than 580 g/mol.

4. A photoinitiator composition according to any one of claims 1 to 3 wherein the composition further comprises acetonitrile; the acetonitrile accounts for 1-10 wt% of the composition.

5. The photoinitiator composition according to claim 4 wherein the acetonitrile is present in an amount of 3 to 8 wt% of the composition.

6. The photoinitiator composition according to claim 5 wherein the acetonitrile is present in an amount of 4 to 6 wt% of the composition.

7. The photoinitiator composition of claim 5 or 6 further comprising (1-methyldecyl) -benzene.

8. The photoinitiator composition of claim 7 further comprising 1, 2-diiodo-4, 5-dimethylbenzene.

9. The photoinitiator composition of claim 8 further comprising 2- (2-iodophenyl) -2, 3-dihydro-1H-naphtho [1, 2-e ] [1, 3] oxazine.

10. Use of a photoinitiator composition according to any of claims 1 to 9 for the reduction of tack or tack films.